Semiconductor device and method of manufacturing the same

ABSTRACT

Disclosed is a method of manufacturing a semiconductor device, comprising forming a metal compound film directly or indirectly on a semiconductor substrate, forming a metal-containing insulating film consisting of a metal oxide film or a metal silicate film by oxidizing the metal compound film, and forming an electrode on the metal-containing insulating film.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a division of application Ser. No. 09/492,780, filed Jan. 28,2000 (now U.S. Pat. No. 6,737,716), which is incorporated in itsentirety herein by reference. This application is also based upon andclaims priority from prior Japanese Patent Applications No. 11-022688,filed Jan. 29, 1999; No. 11-041343, filed Feb. 19, 1999; and No.11-267207, filed Sep. 21, 1999, the entire contents of which areincorporated herein by reference.

BACKGROUND OF THE INVENTION

The present invention relates to a semiconductor device and a method ofmanufacturing the same, particularly, to improvement in performance ofthe gate insulating film.

With progress in miniaturization of a MOSFET, the gate electrode isrequired to have a lower resistance. Also, in a gate electrode using apolycrystalline silicon (polysilicon), the problem of depletion is notnegligible nowadays. Therefore, it is of high importance to develop agate structure consisting of a metal single layer. Concerning the gateinsulating film, it is proposed to use a film made of a material havinga high dielectric constant, e.g., TiO₂, in place of SiO₂ for decreasingthe equivalent oxide thickness of the gate insulating film.

FIGS. 14A to 14C show a conventional manufacturing process. In the firststep, a TiO₂ film 502 is formed as a gate insulating film by a LP-CVDmethod in a thickness of about 10 nm on a silicon substrate 500, asshown in FIG. 14A. Used as the CVD gas is, for example,Ti(C₁₁H₁₉O₂)₂Cl₂. Then, a TiN film 503 in a thickness of 10 to 20 nm isformed on the TiO₂ film 502 by a CVD method under a gaseous atmosphereof TiCl₄ and NH₃ as shown in FIG. 14B. The TiN film 503 acts as abarrier metal layer serving to prevent diffusion of a gate electrodematerial into the gate insulating film or to control the work function.Further, a metal electrode 504 consisting of W, Al, Cu, etc. is formedby CVD on the TiN film 503, as shown in FIG. 14C.

However, the conventional method described above gives rise to a seriousproblem. Specifically, it is difficult to form the TiO₂ film. 502 havingoxygen supplied thereinto completely in the step shown in FIG. 14A.Since the oxygen shortage functions as a donor in the TiO₂ film 502, theinsulating properties of the TiO₂ film are markedly deteriorated by aslight oxygen shortage. It should also be noted that the impuritiescontained in the CVD gas such as carbon and chlorine are left unremovedso as to cause the oxygen shortage. Further, the CVD film tends tobecome lower in density than the oxide film formed by thermal oxidation,as can be seen from CVD of a silicon oxide film. As a result, an oxygenshortage tends to be caused. Such being the situation, it is difficultto form a transistor having good characteristics and a high reliability.

On the other hand, the TiO₂ film 502 constituting the conventional gateinsulating film leaves room for further improvement in the filmstructure. FIGS. 15A and 15B schematically show the film structure ofthe TiO₂ film 502, wherein FIG. 15A is a cross sectional view, and FIG.15B is a plan view.

In forming the TiO₂ film 502 in the step shown in FIG. 14A, a clearcrystal grain boundary 512 is formed between adjacent crystal grains 511of TiO₂, as shown in FIGS. 15A and 15B. As a result, the electricalinsulating properties of the TiO₂ film constituting the gate insulatingfilm are markedly deteriorated, making it very difficult to prepare aMIS transistor having good characteristics and a high reliability.

BRIEF SUMMARY OF THE INVENTION

An object of the present invention is to provide a. semiconductor devicein which insulating properties of the insulating film such as a gateinsulating film are improved so as to improve the characteristics andreliability of the semiconductor device and a method of manufacturingthe particular semiconductor device.

According to a first aspect of the present invention, there is provideda method of manufacturing a semiconductor device, comprising:

forming a metal compound film directly or indirectly on a semiconductorsubstrate;

forming a metal-containing insulating film consisting of a metal oxidefilm or a metal silicate film by oxidizing the metal compound film; and

forming an electrode on the metal-containing insulating film.

In the first aspect of the present invention, the metal-containinginsulating film may consist of a plurality of first insulating regionsformed of grains containing a metal oxide of a metal elementconstituting the metal compound film and a second insulating regionformed of an amorphous insulating material in a region except the firstinsulating regions.

According to a second aspect of the present invention, there is provideda semiconductor device, comprising:

a semiconductor substrate;

a metal-containing insulating film formed directly or indirectly on thesemiconductor substrate, the metal-containing insulating film consistingof a plurality of first insulating regions formed of grains containing ametal oxide and a second insulating region formed of an amorphousinsulating material in a region except the first insulating regions; and

an electrode formed on the metal-containing insulating film.

According to a third aspect of the present invention, there is provideda semiconductor device, comprising:

a first metal oxide film formed directly or indirectly on asemiconductor substrate;

a second metal oxide film formed on the first metal oxide film; and

a gate electrode formed on the second metal oxide film,

wherein, the decrease of the Gibbs free energy at the time when a metalconstituting the gate electrode forms an oxide is larger than that atthe time when a metal constituting the first metal oxide film forms anis oxide, and the decrease of the Gibbs free energy at the time when ametal constituting the second metal oxide film forms an oxide is largerthan or equal to that at the time when the metal constituting the gateelectrode forms an oxide.

According to a fourth aspect of the present invention, there is provideda semiconductor device, comprising:

a semiconductor substrate having a trench;

a metal-containing insulating film consisting of a metal oxide film or ametal silicate film and formed along the inner surface of the trench,the metal-containing insulating film constituting a gate insulatingfilm; and

a gate electrode formed on the metal-containing insulating film,

wherein a thickness A of the metal-containing insulating film in thecenter of the bottom portion, a thickness B of the metal-containinginsulating film in the center of the side wall portion, and a thicknessC of the metal-containing insulating film at the corner portion along aline joining the intersection between the bottom portion and the sidewall portion of the trench and the intersection between the uppersurface and the side wall surface of the metal-containing insulatingfilm meet the relationship C²>(A²+B²).

According to a fifth aspect of the present invention, there is provideda semiconductor device, comprising:

a semiconductor substrate;

a gate insulating film formed on the semiconductor substrate;

a gate electrode formed on the gate insulating film;

a side wall insulating film formed along a side wall of the gateelectrode;

a metal oxide film formed on the upper surface of the gate electrode;

diffusion layers formed within those portions of the semiconductorsubstrate which are positioned on both sides of the gate electrode;

source-drain regions formed on the diffusion layers and in contact withthe side wall insulating film; and

silicide films formed on the source-drain regions, the upper surface ofthe silicide film being substantially flush with the upper surface ofthe metal oxide film.

In the fifth aspect of the present invention, the silicide film containsa noble metal forming a silicide at a temperature lower than the meltingpoint of aluminum. The silicide film contains at least one of palladium,nickel, platinum and cobalt. Also, the gate electrode consists ofaluminum, titanium, zirconium, hafnium, tantalum, niobium, vanadium or anitride of any of these metals.

The present invention also provides semiconductor devices A and B givenbelow and methods C to H of manufacturing a semiconductor device givenbelow:

A. A semiconductor device, comprising:

a gate insulating film formed on a semiconductor substrate;

a gate electrode formed on the gate insulating film;

a side wall insulating film formed along the side wall of the gateelectrode;

source-drain regions formed on those portions of the semiconductorsubstrate which are positioned on both sides of the gate electrode anddo not have a contaminated layer, the source-drain regions having afacet, and the upper surfaces of the source-drain regions beingpositioned higher than the upper surface of the semiconductor substrate;

diffusion layers formed within the semiconductor substrate andpositioned below the source-drain regions; and

silicide films formed on the source-drain regions.

B. A semiconductor device, comprising:

a gate insulating film formed on a semiconductor substrate;

a gate electrode formed on the gate insulating film;

a side wall region formed along the side wall of the gate electrode, theside wall region consisting of a plurality of insulating regionsdiffering from each other in dielectric constant; and

source-drain regions formed on those portions of the semiconductorsubstrate which are positioned on both sides of the gate electrode, theupper surfaces of the source-drain regions being positioned higher thanthe upper surface of the semiconductor substrate.

In semiconductor device B of the present invention, at least one of theplural insulating regions constituting the side wall region is formed ofthe air.

C. A method of manufacturing a semiconductor device, comprising:

forming a first insulating film on a semiconductor substrate;

forming a gate electrode on the first insulating film;

selectively forming a second insulating film on the upper surface of thegate electrode;

forming a third insulating film on the side wall of the gate electrode;

applying a treatment with phosphoric acid so as to selectively removethat portion of the first insulating film which is positioned outsidethe gate electrode and the third insulating film so as to expose thesurface of the semiconductor substrate;

forming an epitaxial layer having a facet on the exposed portion of thesemiconductor substrate;

injecting an impurity into the epitaxial layer to form a first diffusionlayer; and

diffusing the impurity within the first diffusion layer to form a seconddiffusion layer in a surface region of the semiconductor substrate.

In the manufacturing method C of the present invention, the treatmentwith phosphoric acid should be carried out at a temperature fallingwithin a range of between room temperature and 180° C. Preferably, thephosphoric acid treatment should be carried out at 160° C.

D. A method of manufacturing a semiconductor device, comprising:

forming a first insulating film on a semiconductor substrate;

forming a dummy gate on the first insulating film;

forming a second insulating film on the side surface of the dummy gate;

applying a treatment with phosphoric acid to selectively remove thatportion of the first insulating film which is positioned outside thedummy gate and the second insulating film so as to expose the surface ofthe semiconductor substrate;

forming an epitaxial layer having a facet on the exposed semiconductorsubstrate;

implanting impurity ions into the epitaxial layer to form a firstdiffusion layer;

diffusing the impurity within the first diffusion layer to form a seconddiffusion layer in a surface region of the semiconductor substrate;

forming a silicide film on the first diffusion layer;

forming an interlayer insulating film;

flattening the interlayer insulating film to expose the surface of thedummy gate;

removing the dummy gate and the first insulating film to form anopening;

forming a gate insulating film within the opening;

forming a reaction preventing film on the gate insulating film;

forming a metal film on the reaction preventing film; and

flattening the gate insulating film, the reaction preventing film andthe metal film to expose the surface of the interlayer insulating film.

In the manufacturing method D of the present invention, the gateinsulating film consists of a tantalum oxide film, the reactionpreventing film consists of a titanium nitride film, and the metal filmconsists of an aluminum film.

E. A method of manufacturing a semiconductor device, comprising:

forming a dummy gate on a semiconductor substrate;

forming a first side wall insulating film on the side wall of the dummygate;

forming an epitaxial layer on the exposed surface of the semiconductorsubstrate;

injecting an impurity into the epitaxial layer to form a first diffusionlayer;

forming a second side wall insulating film on the side surface of thefirst side wall insulating film;

forming a third side wall insulating film on the side surface of thesecond side wall insulating film;

injecting an impurity into the semiconductor substrate to form a seconddiffusion layer;

forming a first interlayer insulating film;

flattening the first interlayer insulating film to expose the surface ofthe dummy gate;

removing the dummy gate to form a first trench;

forming a gate insulating film within the first trench; and

forming a gate electrode on the gate insulating film.

The manufacturing method E of the present invention further comprisesremoving the first and third side wall insulating films to form secondand third trenches after formation of the gate electrode andsubsequently forming a second interlayer insulating film.

F. A method of manufacturing a semiconductor device, comprising:

forming a dummy gate on a semiconductor substrate;

forming a first side wall insulating film on the side wall of the dummygate;

forming a first epitaxial layer in contact with the first side wallinsulating film on the exposed surface of the semiconductor substrate;

injecting an impurity into the first epitaxial layer to form a firstdiffusion layer;

forming a second side wall insulating film on the side surface of thefirst side wall insulating film;

forming a third side wall insulating film on the side surface of thesecond side wall insulating film;

forming a second epitaxial layer on the first diffusion layer;

injecting an impurity into the second epitaxial layer to form a seconddiffusion layer;

forming a first interlayer insulating film;

flattening the first interlayer insulating film to expose the surface ofthe dummy gate;

removing the dummy gate to form a first trench;

forming a gate insulating film within the first trench;

forming a gate electrode on the gate insulating film;

removing the first and third side wall insulating films to form secondand third trenches, respectively; and

forming a second interlayer insulating film.

In the manufacturing method F of the present invention, the secondinterlayer insulating film may be formed to fill the second and thirdtrenches or to form free spaces within the second and third trenches.

G. A method of manufacturing a semiconductor device, comprising:

forming a gate insulating film on a semiconductor substrate;

forming a gate electrode on the gate insulating film;

forming a first side wall insulating film on the side surface of thegate electrode;

forming an epitaxial layer on the exposed surface of the semiconductorsubstrate;

injecting an impurity into the epitaxial layer to form a first diffusionlayer;

forming a second side wall insulating film on the side surface of thefirst side wall insulating film;

forming a third side wall insulating film on the side surface of thesecond side wall insulating film; and

injecting an impurity into the semiconductor substrate to form a seconddiffusion layer.

H. A method of manufacturing a semiconductor device, comprising:

forming a insulating film on a entire surface of a semiconductorsubstrate provided with source-drain regions;

flattening the insulating film to expose the surface of the source-drainregions; and

selectively converting the surface region of the exposed portion of thesource-drain regions into a silicide film.

In the manufacturing method H of the present invention, upper portionsof the source-drain regions may be formed of an epitaxial layer.

In the manufacturing method H of the present invention, formation of thesilicide film may include the steps of, forming a first metal film on aentire surface of the substrate after exposing the surface of thesource-drain regions, applying a heat treatment to cause reactionbetween the source-drain regions and the first metal film, and removingthe unreacted first metal film. It is possible for the unreacted firstmetal film to be removed by a CMP method.

In the manufacturing method H of the present invention, furthercomprises oxidizing an upper surface of a gate electrode formed of asecond metal film different from the first metal film, before formingthe silicide film.

In the manufacturing method H of the present invention, the first metalfilm is formed of a noble metal forming a silicide at a temperaturelower than the melting point of aluminum. The first metal film includespalladium, nickel, platinum and cobalt. Also, the first metal film maybe formed of an alloy containing at least one of these metals. Further,the second metal film is formed of aluminum, titanium, zirconium,hafnium, tantalum, niobium, vanadium or a nitride of any of thesemetals.

Additional objects and advantages of the invention will be set forth inthe description which follows, and in part will be obvious from thedescription, or may be learned by practice of the invention. The objectsand advantages of the invention may be realized and obtained by means ofthe instrumentalities and combinations particularly pointed outhereinafter.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING

The accompanying drawings, which are incorporated in and constitute apart of the specification, illustrate presently preferred embodiments ofthe invention, and together with the general description given above andthe detailed description of the preferred embodiments given below, serveto explain the principles of the invention.

FIGS. 1A to 1C are cross sectional views showing a method ofmanufacturing a semiconductor device according to embodiment 1(A) of thepresent invention;

FIGS. 2A to 2E are cross sectional views showing a method ofmanufacturing a semiconductor device according to embodiment 1(B) of thepresent invention;

FIGS. 3A to 3F are cross sectional views showing a method ofmanufacturing a semiconductor device according to embodiment 1(C) of thepresent invention;

FIGS. 4A to 4E schematically show the effect produced by the method ofmanufacturing a semiconductor device according to embodiment 1(C) of thepresent invention;

FIGS. 5A to 5C are cross sectional views showing a method ofmanufacturing a semiconductor device according to embodiment 1(D) of thepresent invention;

FIGS. 6A and 6B schematically show the structure of the insulating filmaccording to embodiment 2(A) of the present invention;

FIGS. 7A and 7B schematically show the structure of the insulating filmaccording to embodiment 2(B) of the present invention;

FIGS. 8A to 8C are cross sectional views showing the steps for formingan insulating film according to embodiment 2(C) of the presentinvention;

FIG. 9 is a cross sectional view showing another example of theinsulating film according to embodiment 2(C) of the present invention;

FIGS. 10 to 10C are cross sectional views showing the steps for formingan insulating film according to embodiment 2(D) of the presentinvention;

FIG. 11 is a cross sectional view showing another example of theinsulating film according to embodiment 2(D) of the present invention;

FIG. 12 is a graph showing the relationship between the oxidizingtemperature of a TiN film and the crystal grain diameter of TiO₂,covering the case where the thickness of the TiO₂ film is changed;

FIGS. 13A to 13C schematically show the structure of the TiO₂ film atpoints A, B and C shown in FIG. 12;

FIGS. 14A to 14C are cross sectional views showing a conventional methodof manufacturing a semiconductor device.;

FIGS. 15A and 15B schematically show the structure a conventionalinsulating film;

FIGS. 16A to 16D are cross sectional views showing a method ofmanufacturing a semiconductor device according to embodiment 3(A) of thepresent invention;

FIGS. 17A to 17M are cross sectional views showing a method ofmanufacturing a semiconductor device according to embodiment 3(B) of thepresent invention;

FIGS. 18A to 18M are cross sectional views showing a method ofmanufacturing a semiconductor device according to embodiment 4(A) of thepresent invention;

FIGS. 19A to 19D are cross sectional views showing another example of amethod of manufacturing a semiconductor device according to embodiment4(A) of the present invention;

FIGS. 20A and 20B are cross sectional views showing another example of amethod of manufacturing a semiconductor device according to embodiment4(A) of the present invention;

FIGS. 21A and 21B are cross sectional views showing another example of amethod of manufacturing a semiconductor device according to embodiment4(A) of the present invention;

FIGS. 22A to 20F are cross sectional views showing a method ofmanufacturing a semiconductor device according to embodiment 4(B) of thepresent invention;

FIGS. 23A to 23J are cross sectional views showing another example of amethod of manufacturing a semiconductor device according to embodiment 5of the present invention;

FIG. 24 is a cross sectional view showing a morphological deteriorationat the interface between a silicon layer and a silicide layer; and

FIG. 25 is a graph showing the relationship between the amount of chargeinjected into the gate insulating film and the cumulative failure.

DETAILED DESCRIPTION OF THE INVENTION

Embodiment 1 of the present invention will now be described withreference to the accompanying drawings.

Embodiment 1(A)

FIGS. 1A to 1C are cross sectional views showing a method ofmanufacturing a semiconductor device according to embodiment 1(A) of thepresent invention.

In the first step, a thin TiN film 11 having a thickness of about 2 nmis formed on a silicon substrate 10, as shown in FIG. 1A. The TiN film11 is formed by a CVD method under a mixed gas atmosphere containingTiCl₄ and NH₃. In addition to the TiCl₄/NH₃ mixed gas, TiI₄/NH₃ mixedgas and TiBr₄/NH₃ mixed gas can also be used. Further, the followingmixed gases can also be used in the present invention:

(C₅H₅)(C₈H₈)Ti/NH₃ mixed gas;

(C₅H₅)₂Ti[N(CH₃)₂]₂/NH₃ mixed gas;

(C₅H₅)₂TiCl₂/NH₃ mixed gas;

[(CH₃)₃SiCH₂]₄Ti/NH₃ mixed gas;

Ti[N(CH₃)₂]₄ series gas;

Ti[N(C₂H₅)₂]₄ series gas;

(C₅H₅)₂Ti(N₃)₂ series gas.

In the case of using the last three gases, a TiN film can be formedwithout using a nitriding agent such as NH₃ or N radical, though it ispossible to use a nitriding agent in forming a TiN film. It is alsopossible to form the TiN film by a sputtering method using a Ti targetor a Ti target containing N. In this case, used is a plasma of a mixedgas containing Ar, Kr or Xe gas and a N-containing gas such as N₂ gas.Further, the TiN film can be formed by a vacuum vapor deposition method.Where a sputtering method is employed, the energy of the ions such as Arions for sputtering the target and the energy of the particles liberatedfrom the target should be not higher than 100 eV, preferably not higherthan 50 eV, and more preferably not higher than 20 eV. In this case, thedamage done to the film surface can be diminished to form a gateinsulating film having a higher reliability.

In the next step, the TiN film 11 is oxidized by a heat treatment underan O₂ atmosphere, an O₃ atmosphere, an oxygen radical atmosphere or asteam atmosphere to form a TiO₂ film 12 having a thickness of about 4nm, as shown in FIG. 1B. It is possible to apply the oxidizing treatmentexcessively to form a silicon oxide film at the boundary between thesilicon substrate 10 and the TiO₂ film 12.

Where a thicker TiO₂ film (about 20 nm thick) is required, it ispossible to oxidize a TiN film having a thickness of about 10 nm to forma TiO₂ film having a thickness of about 20 nm. However, the presentinventors have found through experiments that the decrease in thethickness of the TiN film facilitates out-diffusion of nitrogengenerated during the oxidizing treatment or chlorine or carbon mixed inthe TiN film during the film formation. In other words, it has beenfound that a high quality TiO₂ film free from impurities and oxygenshortage can be obtained if the thickness of the TiN film is decreased.It has also been found that, with increase in the thickness of the TiO₂film, large crystal grains tend to exist in the TiO₂ film so as todeteriorate the surface morphology.

Where it is desired to form a thick TiO₂ film, a high quality TiO₂ filmcan be obtained by repeating the process of forming a TiN film having athickness of about 2 nm and the process of oxidizing the TiN film. Forexample, a TiO₂ having a thickness of about 20 nm can be obtained byrepeating 5 times the process of forming a TiN film about 2 nm thick andthe oxidizing process.

The impurity content can be lowered by increasing the oxidizingtemperature. However, the crystal grain diameter of the TiO₂ film isenlarged with increase in the oxidizing temperature. The increase in thecrystal grain diameter deteriorates the surface morphology. Such beingthe situation, it is desirable to carry out the oxidizing treatment at atemperature not higher than 500° C. The impurity content of the formedfilm is certainly increased if the oxidizing temperature is lowered.However, the impurities can be out-diffused by setting the thickness ofthe TiN film at 5 nm or less, preferably at 2 nm or less.

Then, a TiN film 13 acting as a barrier metal layer is formed by a CVDmethod, followed by forming a desired metal layer as a gate electrode14, as shown in FIG. 1C.

This embodiment is featured in that the TiN film 11 is formed and, then,oxidized to form the TiO₂ film 12. Unlike the conventional TiO₂ filmformed directly by a CVD method, the TiO₂ film is formed by thermaloxidation in this embodiment of the present invention. As a result, theTiO₂ film free from oxygen deficiency and having a high reliability canbe obtained. Further, by setting the thickness of the TiN film at 5 nmor less, preferably 2 nm or less, the impurities generated during theoxidizing process such as nitrogen, carbon and chlorine can beout-diffused easily.

Incidentally, it is already reported that an Al₂O₃ layer is formed bythermal oxidation of an Al layer. In this technique, however, Al reactswith the underlying silicon substrate or a silicon oxide film during thethermal oxidation of the Al layer. In the present invention, however,silicon is not diffused into the TiN film, and the TiN film does notreact with the underlying silicon substrate, making it possible to forma TiO₂ film without bringing about reaction with the silicon substrateduring the thermal oxidation process. It follows that it is possible toavoid problems such as an increased roughness of the boundary betweenthe gate insulating film and the silicon substrate that is caused by thesilicide reaction with the silicon substrate.

In oxidizing the TiN film 11 in the process shown in FIG. 1B; it ispossible for a silicon oxide film to be formed at the boundary betweenthe silicon substrate 10 and the TiO₂ film 12 and to have an excessivelylarge thickness, if the oxidization is performed excessively. To preventthe problem, it is desirable to form in advance a very thin siliconoxynitride film about 1 nm thick on the silicon substrate 10. Thesilicon oxynitride film thus formed prevents the silicon substrate 10from being oxidized. Alternatively, it is possible to form a siliconoxide film in place of the silicon oxynitride film.

In this embodiment, the TiN film 11 is oxidized to form the TiO₂ film.However, the present invention is featured in that a metal compound filmthat does not react with the silicon substrate is formed and thermallyoxidized to form a metal oxide film. Therefore, a TiC film can be usedin place of the TiN film.

It is also possible to use a TiON film or a TiONC film. Since a filmhaving small crystal grains or an amorphous film can be formed byallowing the TiN film to contain oxygen or carbon, the surfacemorphology is improved. Naturally, the TiO₂ film obtained by oxidizingthe TiON film or a TiONC film exhibits an improved surface smoothness.

A mixed gas containing TiCl₄, NH₃ and O₂, a mixed gas containing TiI₄,NH₃ and O₂ and a mixed gas containing TiBr₄, NH₃ and O₂ can be used forforming the TiON film. For forming the TiNC film, it is possible to usean organic gas containing C including, for example, the gases givenbelow:

(C₅H₅)(C₈H₈)Ti/NH₃ mixed gas;

(C₅H₅)₂Ti[N(CH₃)₂]₂/NH₃ mixed gas;

(C₅H₅)₂TiCl₂/NH₃ mixed gas;

[(CH₃)₃SiCH₂]₄Ti/NH₃ mixed gas;

Ti[N(CH₃)₂]₄ series gas;

Ti[N(C₂H₅)₂]₄ series gas;

(C₂H₅)₂Ti(N₃)₂ series gas.

For forming the TiONC film, it is possible to use the above organic gasby adding oxygen gas.

It is also possible to employ a sputtering method using a Ti target or aTi target containing O, N or C. In this case, used is a plasma of amixed gas containing Ar, Kr or Xe gas and O or N. Where a sputteringmethod is employed, the energy of the ions such as Ar ions forsputtering the target and the energy of the particles liberated from thetarget should be not higher than 100 eV, preferably not higher than 50eV, and more preferably not higher than 20 eV. In this case, the damagedone to the film surface can be diminished to form a gate insulatingfilm having a higher reliability.

It is also possible to form the TiO₂ film by oxidizing an oxygendeficient TiO_(2-x) film. In this case, the effect described previouslycan also be obtained because the TiO₂ film is formed by thermaloxidation. The CVD gas source used for forming the TiO film or TiO_(2-x)film includes, for example:

Ti(C₁₁H₁₉O₂)Cl₂ series gas;

Ti(OC₂H₅)₄ series gas;

Ti(i-OC₃H₇)₄ series gas;

Ti(OCH₃)₄ series gas; and

Ti(n-OC₄H₉)₄ series gas.

The TiO_(2-x) film can be formed under temperatures falling within arange of between 400° C. and 750° C. It should be noted that the aboveCVD gas sources can be used by adding NH₃ gas for forming the TiONCfilm,

A TiO₂ film was formed in this embodiment. However, a merit similar tothat in this embodiment can be obtained in the case of using a metalnitride film that does not react with the underlying silicon substratelike the TiN film. For example, a ZrN film, a HfN film, a TaN film or aNbN film can be used in place of the TiN film, and such a metal nitridefilm can be oxidized to form a ZrO₂ film, a HfO₂ film, a Ta₂O₅ film or aNb₂O₅ film. In the case of using the ZrO₂ film, HfO₂ film, Ta₂O₅ film orNb₂O₅ film as a gate insulating film, additional merits can be obtainedas summarized below:

ZrO₂ film: The gate electrode can be formed of not only TiN but also ZrNthat does not react with the gate insulating film made of ZrO₂. ZrN hasa work function smaller than that of TiN. Thus, if a ZrN gate electrodeis used in an n-type MOSFET requiring a low threshold voltage V_(th),the threshold voltage V_(th) can be further lowered, compared with then-type MOSFET using a TiN gate electrode. Further, the band gap for ZrO₂is 8 eV in contrast to 3 eV for TiO₂. Therefore, a thin film exhibitinggood insulating properties can be obtained.

HfO₂ film: The gate electrode can be formed of not only TiN and ZrN butalso HfN that does not react with the gate insulating film made of HfO₂.HfN has a work function smaller than that of TiN or ZrN. Thus, if a HfNgate electrode is used in an n-type MOSFET requiring a low thresholdvoltage V_(th), the threshold voltage V_(th) can be further lowered,compared with the n-type MOSFET using a TiN or ZrN gate electrode.Further, the band gap for HfO₂ is 8 eV, which is equal to that for ZrO₂.Therefore, a thin film exhibiting good insulating properties can beobtained.

Ta₂O₅ film: A Ta₂O₅ film is a film having a high dielectric constant,which is being studied most vigorously nowadays. It is possible for theTa₂O₅ film to lower the expenses for the development, compared with theother metal oxide films noted above.

Nb₂O₅ film: The properties of a Nb₂O₅ film are substantially equal tothose of the Ta₂O₅ film. Thus, the technology for the Ta₂O₅ film can beemployed as it is for the Nb₂O₅ film.

It is also possible to use aluminum, yttrium and cerium in addition totitanium, zirconium, hafnium, tantalum and niobium noted above. Further,these metals can be used in combination. Particularly, yttrium can beused in combination with zirconium to form an insulating film called YSZ(Yttrium Stabilized Zirconia).

In this embodiment of the present invention, a metal compound film suchas TiN film is thermally oxidized to form a metal oxide film such as aTiO₂ film. Alternatively, it is also possible to allow a metal compoundfilm such as a TiN film to contain silicon and to thermally oxidize thesilicon-containing metal compound film to form a metal silicate film. Inthis case, it is possible to use various metal compounds and metaloxides described previously. Also, the metal silicate film can be formedby a method similar to that described in this embodiment of the presentinvention.

The metal silicate film includes a mode in which the metal oxide and thesilicon oxide form separate phases and are present together in the formof a mixture and another mode in which metal such as Ti, silicon, andoxygen are present uniformly in the form of a compound such as TiSiO₄. Ametal silicate film of any of these modes can be obtained by settingappropriately the oxidizing condition, the composition, the thickness,etc. of the metal compound film containing silicon.

Embodiment 1(B)

In this embodiment, a metal oxide film capable of a chemical reactionwith an electrode does not react with the electrode.

FIGS. 2A to 2E are cross sectional views showing a method ofmanufacturing a semiconductor device according to this embodiment of thepresent invention.

In the first step, a very thin silicon oxide film 21 about 1 nm thick isformed on a silicon substrate 20 by thermally oxidizing the siliconsubstrate 20, followed by forming a Ta₂O₅ film 22 about 10 nm thick onthe silicon oxide film 21, as shown in FIG. 2A. The Ta₂O₅ film 22, whichis a high dielectric constant film and acting as a gate insulating film,is formed by the method described previously in conjunction withembodiment 1(A). To reiterate, a TaN film is formed first, followed byoxidizing the TaN film to form the Ta₂O₅ film 22. It is possible to usea silicon oxynitride film about 1 nm thick in place of the silicon oxidefilm 21. The silicon oxynitride film is formed under a gaseousatmosphere containing N₂O, NO or NH₃. It is also possible to form theTa₂O₅ film 22 directly on the silicon substrate 20.

In the next step, a thin TiN film 23 about, for example, 4 nm thick isformed on the Ta₂O₅ film 22 by the method described previously inconjunction with embodiment 1(A), as shown in FIG. 2B, followed byoxidizing the TiN film 23 to form a TiO₂ 24, as shown in FIG. 2C. Then,a TiN film 25 acting as a barrier metal layer is formed on the TiO₂ film24 in order to prevent the gate electrode material from being diffusedinto the gate insulating film or to control the work function, as shownin FIG. 2D. Further, a gate metal electrode 26 consisting of Al, W, Cu,Ag, etc. is formed by a CVD method, a sputtering method or a platingtreatment, as shown in FIG. 2E.

As described above, a thin TiO₂ film 24 is formed on the Ta₂O₅ film 22,followed by forming the TiN film 25 on the TiO₂ film 24. The particularmethod permits avoiding a problem taking place where the TiN film 25 isformed directly on the Ta₂O₅ film 22, i.e., the problem that a reactionto form TiO₂ and TaN proceeds at the TiN/Ta₂O₅ interface, with theresult that the Ta₂O₅ film 22 is reduced to lose the insulatingproperties. The reducing reaction is brought about because decrease inthe Gibbs free energy at the time when Ti contained in the TiN film 25forming the electrode forms an oxide is larger than that at the timewhen Ta contained in the Ta₂O₅ film 22 forms an oxide. In order toprevent the gate insulating film from being deteriorated by the reducingreaction, it is necessary for the decrease in the Gibbs free energy atthe time when the metal forming the electrode forms an oxide to be equalto or smaller than that at the time when the metal contained in the gateinsulating film forms an oxide.

In this embodiment, the thin TiO₂ film 24 that does not react with theelectrode is interposed between the TiN film 25 constituting theelectrode and the Ta₂O₅ film 22 acting as a gate insulating film so asto avoid the problem pointed out above. It should be noted that themetal contained in TiO₂ is equal to the metal contained in TiN. As aresult, the decrease in Gibbs free energy at the time when the metalconstituting the electrode forms an oxide is equal to that at the timewhen the metal contained in the uppermost layer of the gate insulatingfilm forms an oxide, making it possible to prevent the reducing reactionof the insulating film positioned below the electrode.

Embodiment 1(C)

This embodiment is directed to a transistor using the gate structuredescribed in conjunction with embodiments 1(A) and 1(B).

FIGS. 3A to 3F are cross sectional views showing the process ofmanufacturing a semiconductor device according to this embodiment of thepresent invention.

In the first step, an element isolating region 31 is formed by, forexample, an STI technology on a silicon substrate 30, as shown in FIG.3A. Then, a laminate structure consisting of a gate oxide film 32 about6 nm thick, a polysilicon film 33 about 150 nm thick and a siliconnitride film 34 about 50 nm thick is formed by an oxidizing technology,a CVD technology, a lithography technology and a RIE technology. Thelaminate structure forms a dummy gate structure that is to be removedlater. Then, an extension diffusion layer 35 is formed by ionimplantation, followed by forming a gate side wall consisting of asilicon nitride film 36 having a width of about 40 nm by a CVDtechnology and a RIE technology.

In the next step, source-drain diffusion layers 37 are formed by ionimplantation, followed by forming metal silicide (CoSi₂ or TiSi₂) layers38 each having a thickness of about 40 nm selectively within thesource-drain regions by a salicide technology using the dummy gate as amask, as shown in FIG. 3B. Then, an interlayer insulating film 39consisting of SiO₂ is formed by a CVD method, followed by flattening theSiO₂ film 39 by a CMP technology to expose the surfaces of the siliconnitride films 34 and 36, as shown in FIG. 3C.

In the next step, the silicon nitride film 34 is selectively removedwith, for example, phosphoric acid, with the interlayer insulating film39 left unremoved, as shown in FIG. 3D. In this step, the siliconnitride film 36 is also etched to make the upper surface of the siliconnitride film 36 flush with the upper surface of the polysilicon film 33.Then, the polysilicon film 33 is selectively removed by a radical atometching technology with the interlayer insulating film 39 and thesilicon nitride film 36 left unremoved. Further, the dummy gate oxidefilm 32 is removed by a wet etching using, for example, hydrofluoricacid so as to open the gate-forming region.

In the next step, a gate insulating film 40 consisting of a materialhaving a high dielectric constant and a gate electrode 41 are formed bythe method described previously in conjunction with embodiments 1(A) and1(B), as shown in FIG. 3E. Finally, the gate insulating film 40 and thegate electrode 41 are flattened by a CMP technology until the interlayerinsulating film 39 is exposed to the outside, as shown in FIG. 3F, so asto finish preparation of a MOSFET in which the gate insulating film 40is formed of a material having a high dielectric constant, the gateelectrode 41 is formed of a metal, and the source-drain regions areformed of a metal silicide.

A prominent merit can be obtained where the method of forming a gateinsulating film described previously in conjunction with embodiments1(A) and 1(B) is applied to the damascene gate process shown FIGS. 3A to3F.

FIG. 4A schematically shows a trench defined by a silicon substrate 50forming the bottom of the trench and by an insulating film 51 formingthe side surface of the trench. The structure shown in FIG. 4Acorresponds to the step shown in FIG. 3D and, thus, a gate insulatingfilm and a gate electrode are buried in the trench.

If a TiO₂ film is formed as a gate insulating film 53 within the trenchby the conventional CVD method, the entire region of the gate insulatingfilm 53 has a uniform thickness A as shown in FIG. 4B even in the caseof employing a CVD technology that permits producing the mostsatisfactory coverage characteristics. Therefore, it is impossible forthe thickness C in the corner portion to be greater than 2^(1/2) timesas much as the thickness A in the bottom portion. In the corner portion,the electric field is concentrated by the voltage applied to the gateelectrode and, thus, the gate breakdown voltage tends to beunsatisfactory.

In this embodiment of the present invention, however, a TiN film isformed first by, for example, a CVD method, followed by oxidizing theTiN film into the TiO₂ film 53. Since a TiO₂ film about twice as thickas the TiN film can be obtained by oxidation, the thickness C in thecorner portion is larger than 2^(1/2) times the thickness A in thebottom portion, as shown in FIG. 4C. As a result, the electric fieldconcentration in the corner portion is suppressed so as to markedlyimprove the gate breakdown voltage.

Where the thickness of the TiO₂ film 53 in the bottom portion of thetrench differs from that in the side wall portion of the trench as shownin FIG. 4D, the relationship C²>(A²+B²) is generally met, where Arepresents the thickness of the TiO₂ film in the center of the bottomportion, B represents the thickness of the TiO₂ film in the center ofthe side wall portion, and C represents the thickness of the TiO₂ filmin the corner portion along a line joining the intersection between thebottom portion and the side wall portion of the trench and theintersection between the upper surface and the side wall surface of theTiO₂ film. In short, the thickness C in the corner portion in thisembodiment is larger than the thickness C′ in the corner portion in theprior art.

Incidentally, where the bottom portion of the TiO₂ film 53 bites theouter insulating film 51, the biting portion is neglected and thethickness C of the corner portion is defined as shown in FIG. 4E.

Embodiment 1(D)

The present invention can be applied not only to the gate insulatingfilm but also to various capacitor structures, e.g., to a trenchcapacitor of a DRAM cell.

FIGS. 5A to 5C are cross sectional views showing the process for forminga DRAM cell having a trench capacitor formed therein.

In the first step, a trench 61 is formed by etching in a siliconsubstrate 60, followed by forming an n-type diffusion layer 62 on theinner wall of the trench by means of a gaseous phase diffusion ofarsenic (As), as shown in FIG. 5A. Then, a TiO₂ film 63 is formed alongthe inner wall of the trench 61 by the method of the present invention,followed by filling the trench 61 with a polysilicon film 64, as shownin FIG. 5B. To be more specific, a thin TiN film is formed on the entiresurface of the substrate including the trench, followed by oxidizing theTIN film into the TiO₂film 63. Then, the polysilicon film 64 isdeposited on the TiO₂ film 63, followed by a flattening, treatment by,for example, a CMP until the substrate surface is exposed to theoutside.

In the next step, an element isolating region 65 is formed, followed byforming a gate oxide film (not shown) and a gate electrode 66, as shownin FIG. 5C. Then, source-drain diffusion layers 67, etc. are formed.

In this embodiment, a capacitor insulating film free from oxygendeficiency and having a high reliability can be obtained because theTiO₂ film 62 is formed by oxidizing a TiN film. Further, since the filmis thickened in the corner portion of the trench, the breakdown voltageof the capacitor insulating film can be improved.

EMBODIMENT 2

Embodiment 2 of the present invention will now be described withreference to the accompanying drawings.

Embodiment 2(A)

FIG. 6A is a cross sectional view showing the construction of aninsulating film 70 for electrical insulation such as a gate insulatingfilm included in a MIS transistor, and FIG. 6B is a plan view of theinsulating film 70 shown in FIG. 6A.

As shown in the drawings, the insulating film (metal-containinginsulating film) 70 constitutes structure A consisting of a plurality offirst insulating regions 71 formed of grains containing a metal oxideand a second insulating region 72 formed of an amorphous insulatingmaterial in the region except the first insulating regions 71.

Structure A is formed by method A comprising forming a metal compoundfilm directly or indirectly on a semiconductor substrate, and oxidizingthe metal compound film to form the insulating film (metal-containinginsulating film) 70 consisting of a plurality of first insulatingregions 71 formed of grains containing an oxide of a metal elementcontained in the metal compound film and a second insulating region 72formed of an amorphous insulating material in the region except thefirst insulating regions 71.

Since the insulating film 70 consists of the first insulating regions 71and the second insulating region 72, the crystal grains contained in thefirst insulating regions 71 are not brought into direct contact so as toeliminate a clear crystal boundary between the crystal grains. Thismakes it possible to suppress the leakage current through the insulatingfilm 70 and to suppress deterioration of the insulating properties. Itfollows that the characteristics and reliability can be improved byusing the insulating film 70 as, for example, a gate insulating film ofa MIS transistor.

Structures B, C, D and methods B, C, D given below constitute preferredembodiments of structure A and method A described above:

Structure B, Method B: The metal compound film contains the metalelement forming the metal oxide and silicon. The first insulating regioncontains a crystal of the metal oxide. The second insulating regioncontains silicon, oxygen and the metal element forming the metal oxide.

Structure C, Method C: The metal compound film contains a first metalelement forming a metal oxide and a second metal element differing fromthe first metal element. The first insulating region contains a crystalof the metal oxide. The second insulating region contains oxygen and thesecond metal element.

Structure D, Method D: The metal compound film contains a metal elementforming the metal oxide. The first insulating region is formed of acrystal grain of the metal oxide. The second insulating region is formedof an amorphous region of the metal oxide.

Structures (1) to (11) and methods (1) to (11) given below constitutepreferred embodiments of structures A-D and methods A-D given above:

(1) In structure B and method B, the first insulating region is formedof only crystal grains of a metal oxide, or contains crystal grains ofthe metal oxide and amorphous metal oxide.

(2) In structure D and method D, the first insulating region is formedof only a single crystal grain of a metal oxide.

(3) In structure A and method A, the crystal grains constituting thefirst insulating region consist of an aggregate of a plurality of singlecrystals (single crystals of metal oxide), in which the angle formed bythe same crystal face orientations is not larger than 10°, preferablynot larger than 5°. If the angle formed by the single crystals is notlarger than 10°, the crystal grain boundary energy is small even if acrystal grain boundary is formed by mutual contact of the singlecrystals. As a result, the electrical insulating properties are scarcelydeteriorated.

(4) In structure B and method B, the amorphous insulating materialconstituting the second insulating region contains at least a metaloxide equal to that constituting the first insulating region and siliconoxide and also contains as desired at least one of silicon oxynitrideand silicon nitride. Silicon oxide, silicon oxynitride and siliconnitride are readily made amorphous and, thus, adapted for use asmaterials constituting the second insulating region.

(5) In structure C and method C, the crystallizing temperature of thesecond metal oxide containing the second metal element is higher thanthe crystallizing temperature of the first metal oxide containing thefirst metal element. Since the crystallizing temperature of the secondmetal oxide is higher than that of the first metal oxide, the secondmetal oxide tends to be made amorphous easily.

(6) In structure A and method A, used is a metal oxide having adielectric constant higher than that of silicon oxide such as titaniumoxide, zirconium oxide, hafnium oxide, tantalum oxide, niobium oxidealuminum oxide cerium oxide, yttrium oxide or yttrium-zirconium oxide.

(7) In structure A and method A, the metal element contained in themetal oxide and metal compound film includes, for example, titanium,zirconium, hafnium, tantalum, niobium, aluminum, cerium and yttrium.

(8) In structure B and method B, the metal compound film includes ametal nitride film containing silicon, a metal oxynitride filmcontaining silicon, a metal carbonitride film containing silicon, ametal carbide film containing silicon, a metal oxide film containingsilicon, and a metal carboxide film containing silicon.

(9) In structure D and method D, the metal compound film includes ametal nitride film, a metal oxynitride film, a metal carbonitride film,a metal carbide film, a metal oxide film and a metal carboxide film.

(10) In structure D and method D, the thickness of the insulating film70 should be not larger than 10 nm, preferably not larger than 5 nm. Ifthe insulating film 70 is formed thin, the second insulating regionconsisting of an amorphous metal oxide can be formed easily.

(11) In structure A and method A, the insulating film 70 is formed on asilicon substrate, a silicon oxide film, a silicon nitride film or asilicon oxynitride film in the case where the insulating film 70 is usedas a gate insulating film of a MIS transistor. Particularly, if asilicon oxide film, a silicon nitride film or a silicon oxynitride filmhaving a thickness of several atomic layers is formed between thesilicon substrate and the insulating film 70, the interface state can becontrolled easily, making it possible to increase the mobility ofelectrons and holes.

Embodiment 2(B)

FIGS. 7A and 7B relate to embodiment 2(B) and show the construction ofan insulating film for electrical insulation such as a gate insulatingfilm of a MIS transistor. FIG. 7A is a cross sectional view, and FIG. 7Bis a plan view.

In this embodiment, a covering insulating region 73 is formed to coverat least one surface region of a main insulating region 70 a, whichcorresponds to the insulating film 70 shown in FIGS. 6A and 6B,consisting of the first insulating regions 71 and the second insulatingregion 72. In other words, the insulating film 70 consists of the firstinsulating regions 71, the second insulating region 72 and the coveringinsulating region 73. The covering insulating region 73 is formed of anamorphous insulating material equal to that forming the secondinsulating region 72. The first insulating regions 71 and the secondinsulating region 72 are equal to those in embodiment 1.

It is possible for the surface of the main insulating region 70 a to bemade irregular by the presence of the crystal grains contained in thefirst insulating regions 71, resulting in deterioration of morphology.In this embodiment, the deterioration of morphology is suppressed by thepresence of the covering insulating region 73.

Embodiment 2(C)

FIGS. 8A to 8C are cross sectional views showing a process ofmanufacturing a semiconductor device according to embodiment 2(C) of thepresent invention.

In the first step, a silicon-containing TiN film about 2 nm thick isformed as a metal compound layer 81 on a silicon substrate 80, as shownin FIG. 8A. The silicon-containing TiN film 81 can be formed by, forexample, a CVD method under a mixed gas atmosphere containing TiCl₄, NH₃and SiH₄. In addition to the TiCl₄/NH₃/SiH₄ mixed gas, TiI₄/NH₃/SiH₄mixed gas or TiBr₄/NH₃/SiH₄ mixed gas can also be used. Further, themixed gases given below can also be used for forming thesilicon-containing TiN film 81:

(C₅H₅)(C₈H₈)Ti/NH₃/SiH₄ mixed gas;

(C₅H₅)₂Ti[N(CH₃)₂]₂/NH₃/SiH₄ mixed gas;

(C₅H₅)₂TiCl₂/NH₃/SiH₄ mixed gas;

[(CH₃)₃SiCH₂]₄Ti/NH₃ mixed gas;

Ti[N(CH₃)₂]₄/SiH₄ mixed gas;

Ti[N(C₂H₅)₂]₄/SiH₄ mixed gas; and

(C₅H₅)₂Ti(N₃)₂/SiH₄ mixed gas;

In the case of using the last three mixed gases, a TiN film can beformed without using a nitriding agent such as NH₃ or N radicals, thoughit is possible to add a nitriding agent in forming the TiN film.

It is also possible to form a silicon-containing TiN film by asputtering method (or vacuum vapor deposition method) using a Ti targetcontaining silicon, or a Ti target containing both N and Si and a plasmaof a mixed gas containing Ar, Kr or Xe and N such as N₂. Where asputtering method is employed, the energy of the ions such as Ar ionsfor sputtering the target and the energy of the particles liberated fromthe target should be not higher than 100 eV, preferably not higher than50 eV, and more preferably not higher than 20 eV. In this case, thedamage done to the film surface can be diminished to form a gateinsulating film having a higher reliability.

In the next step, the silicon-containing TiN film 81 is oxidized by aheat treatment applied under an O₂ atmosphere, an O₃ atmosphere, anoxygen radical atmosphere, or a steam atmosphere so as to form aninsulating film 82 (gate insulating film) corresponding to structure Bin embodiment 2(A), as shown in FIG. 8B. To be more specific, formed arefirst insulating regions 83 consisting of TiO₂ crystal grains and asecond insulating region 84 consisting of an amorphous insulatingmaterial. At least one of titanium oxide and silicon oxide is containedin the second insulating region 84. In some cases, silicon nitride orsilicon oxynitride is also contained in the second insulating region 84.

It is possible to apply the oxidizing treatment excessively to form asilicon oxide film at the interface between the silicon substrate 80 andthe insulating film 82.

If the silicon-containing TiN film 81 is formed thinner, theout-diffusion of the impurities such as nitrogen generated during theoxidizing treatment as well as chlorine or carbon mixed into thesilicon-containing TiN film 81 during the film formation is facilitatedduring the oxidizing treatment, making it possible to obtain a highquality insulating film low in impurity content. Such being thesituation, it is desirable for the thickness of the silicon-containingTiN film 81 to be not larger than 5 nm, preferably not larger than 2 nm.Where it is desired to form a thick insulating film 82, the process offorming the silicon-containing TiN film 81 having a small thicknessnoted above and the oxidizing process are repeated several times so asto form the insulating film 82 having a desired large thickness.

In the next step, a barrier metal layer 85, e.g., a TiN film, is formedby a CVD method, followed by forming a desired metal film as a gateelectrode film 86 on the barrier metal layer 85, as shown in FIG. 8C.

By the process described above, obtained is a structure in which theinsulating film 82 corresponding to structure B in embodiment 2(A) isused as a gate insulating film.

In the process described above, it is possible to form an amorphousinsulating region in each of the entire upper region and the entirelower region of the insulating film 82, as shown in FIG. 9.

The TiO₂ crystal grain 83 may be a single crystal grain or an aggregateof a plurality of single crystal grains in which the same crystal faceorientations form an angle not larger than 10°, preferably not largerthan 5°. As described previously, where the angle formed by singlecrystal grains is not larger than 10°, the crystal grain interfaceenergy is small and, thus, the insulating properties are scarcelydeteriorated.

Where the silicon-containing TiN film 81 is oxidized excessively, it ispossible for a silicon oxide film to be formed at the interface betweenthe silicon substrate 80 and the insulating film 82 and for the siliconoxide film to have an excessively large thickness. To prevent theproblem, it is desirable to form a very thin silicon oxynitride filmabout 1 nm thick under a gaseous atmosphere containing NO, N₂O, etc. onthe silicon substrate 80 before formation of the silicon-containing TiNfilm 81. The silicon oxynitride film thus formed serves to prevent thesilicon substrate 80 from being oxidized. Alternatively, it is possibleto form a silicon oxide film in place of the silicon oxynitride film.

In this embodiment, the insulating film 82 is formed by oxidizing thesilicon-containing TiN film 81. However, there are variousmodifications.

Titanium is used as a metal element forming the metal oxide contained inthe insulating film 82. In addition to Ti, it is also possible to useZr, Hf, Ta, Nb and Al.

Specifically, a Si-containing TaN film is formed by a CVD method using amixed gas of TaCl₅/NH₃/SiH₄, a mixed gas of TaBr₅/NH₃/SiH₄, or a mixedgas of TaI₅/NH₃/SiH₄, followed by oxidizing the Si-containing TaN film.As a result, formed are first insulating regions 83 containing Ta₂O₅crystal grains and a second insulating region 84 containing tantalumoxide and silicon oxide.

Alternatively, a Si-containing Ta₂O₅ film containing at least 1% of C isformed by a CVD method using a mixed gas of Ta(OC₂H₅)/SiH₄, followed byoxidizing the Ta₂O₅ film with ozone to substitute O for C. As a result,formed are first insulating regions 83 containing Ta₂O₅ crystal grainsand a second insulating region 84 containing tantalum oxide and siliconoxide.

In the case of using niobium, a Si-containing NbN film is formed by aCVD method using a mixed gas of NbCl₅/NH₃/SiH₄, a mixed gas ofNbBr₅/NH₃/SiH₄, or a mixed gas of NbI₅/NH₃/SiH₄, followed by oxidizingthe NbN film. As a result, formed are first insulating regions 83containing Nb₂O₅ crystal grains and a second insulating region 84containing niobium oxide and silicon oxide.

In the case of using zirconium, a Si-containing ZrN film is formed by aCVD method using a mixed gas of ZrCl₄/NH₃/SiH₄, a mixed gas ofZrBr₄/NH₃/SiH₄, a mixed gas of ZrI₄/NH₃/SiH₄, a mixed gas ofZr[N(C₂H₅)₂]₄/NH₃/SiH₄, or a mixed gas of Zr[N(CH₃)₂]₄/NH₃/SiH₄,followed by oxidizing the ZrN film. As a result, formed are firstinsulating regions 83 containing ZrO₂ crystal grains and a secondinsulating region 84 containing zirconium oxide and silicon oxide.

Further, in the case of hafnium, a Si-containing HfN film is formed by aCVD method using a mixed gas of HfCl₄/NH₃/SiH₄, a mixed gas ofHfBr₄/NH₃/SiH₄, or a mixed gas of HfI₄/NH₃/SiH₄, followed by oxidizingthe HfN film. As a result, formed are first insulating regions 83containing HfO₂ crystal grains and a second insulating region 84containing hafnium oxide and silicon oxide.

As described above, the amorphous second insulating region 84 containinga metal oxide and silicon oxide can be formed easily by oxidizing ametal compound film containing silicon and a metal element.

In each of the examples described above, the first insulating regions 83containing crystals of a metal oxide and the second insulating region 84containing a metal oxide and silicon oxide are formed by oxidizing ametal compound film containing silicon and a metal element.Alternatively, an additional method can also be employed.

Specifically, a metal compound film containing a first metal element anda second metal element differing from the first metal element is formedon the silicon substrate 80. The insulating film 82 consisting of aplurality of first insulating regions 83 formed of a metal oxide of thefirst metal element (first metal oxide) and the second insulating region84 formed of an oxide of the second metal element (second metal oxide)can be formed by oxidizing the metal compound film.

In this case, the first and second metal elements should be selectedsuch that the crystallizing temperature of the second metal oxide ishigher than that of the first metal oxide. The first metal oxide formedof crystal grains and the amorphous second metal oxide can be formed bymaking the oxidizing temperature higher than the crystallizingtemperature of the first metal oxide and lower than the crystallizingtemperature of the second metal oxide. It follows that a structuresimilar to that shown in FIGS. 8A to 8C can be obtained.

Embodiment 2(D)

FIGS. 10A to 10C are cross sectional views showing a method ofmanufacturing a semiconductor device according to embodiment 2(D) of thepresent invention.

In the first step, a TiN film is formed in a thickness of 5 nm or less,preferably 2 nm or less, as a metal compound layer 91 on a siliconsubstrate 90, as shown in FIG. 10A. The TiN film 91 can be formed by aCVD method under a mixed gas atmosphere consisting of TiCl₄ and NH₃. Inaddition to the TiCl₄/NH₃ mixed gas, TiI₄/NH₃ mixed gas or TiBr₄/NH₃mixed gas can be used. For forming the TiN film 91, it is also possibleto employ mixed gases given below:

(C₅H₅)(C₈H₈)Ti/NH₃ mixed gas;

(C₅H₅)₂Ti[N(CH₃)₂]₂/NH₃ mixed gas;

(C₅H₅)₂TiCl₂/NH₃ mixed gas;

[(CH₃)₃SiCH₂]₄Ti/NH₃ mixed gas;

Ti[N(CH₃)₂]₄ series gas;

Ti[N(C₂H₅)₂]₄ series gas;

(C₅H₅)₂Ti(N₃)₂ series gas.

In the case of using the last three gases, a TiN film can be formedwithout using a nitriding agent such as NH₃ or N radical, though it ispossible to use a nitriding agent in forming the TiN film.

It is also possible to form a TiN film by a sputtering method (or vacuumvapor deposition method) using a Ti target, or a Ti target containing Nand a plasma of a mixed gas containing Ar, Kr or Xe and N such as N₂.Where a sputtering method is employed, the energy of the ions such as Arions for sputtering the target and the energy of the particles liberatedfrom the target should be not higher than 100 eV, preferably not higherthan 50 eV, and more preferably not higher than 20 eV. In this case, thedamage done to the film surface can be diminished to form a gateinsulating film having a higher reliability.

In the next step, the TiN film 91 is oxidized by a heat treatment atpreferably 500° C. or less under an O₂ atmosphere, an O₃ atmosphere, anoxygen radical atmosphere or a steam atmosphere so as to form aninsulating film 92 (gate insulating film) corresponding to structure Dof embodiment 2(A), as shown in FIG. 10B. Specifically, formed are firstinsulating regions 93 consisting of TiO₂ crystal grains and a secondinsulating region 94 consisting of an amorphous TiO₂ insulatingmaterial.

Since the TiN film 91 is as thin as only 2 nm, the crystallizing energyis very large, compared with the case where the TiN film 91 has a largethickness. Therefore, growth of the crystal grains is suppressed toprevent the grown crystal grains to collide against each other, thoughtit is possible for the grown crystal grains to collide against eachother in the case where the TiN film has a thickness not smaller than 10nm. Since the grown crystal grains do not collide against each other, aclear crystal grain boundary is not formed. It follows that the secondinsulating region 94 consisting of an amorphous TiO₂ is formed betweenadjacent TiO₂ crystal grains (first insulating regions 93).

FIG. 12 is a graph showing the relationship between the oxidizingtemperature of the TiN film and the TiO₂ crystal grain diameter,covering the case where the thickness of the TiO₂ film is changed. FIGS.13A to 13C show the construction of the TiO₂ film at points A, B and Cshown in FIG. 12.

Where the oxidizing temperature is low, TiO₂ crystal grains having alarge grain diameter are unlikely to be formed even if the TiO₂ film hasa large thickness (see point A in FIG. 12). As a result, the TiO₂ filmis constructed as shown in FIG. 13A. Where the thickness of TiO₂ film issmall, TiO₂ crystal grains having a large grain diameter do not groweven if the oxidizing temperature is high (see point B in FIG. 12). As aresult, the TiO₂ film is constructed as shown in FIG. 13B. On the otherhand, where the oxidizing temperature is high and the TiO₂ film has alarge thickness, large TiO₂ crystal grains are grown (see point C inFIG. 12). As a result, a clear crystal grain boundary is formed betweenadjacent TiO₂ crystal grains such that the TiO₂ film is constructed asshown in FIG. 13C. It follows that a TiO₂ film having an amorphousregion formed between adjacent crystal grains and low in leakage currentcan be formed by controlling appropriately the thickness of the TiO₂film and the oxidizing temperature.

Further, a barrier metal layer 95 consisting of, for example, a TiN filmis formed by a CVD method, as shown in FIG. 10C, followed by forming adesired metal film as a gate electrode film 96 on the barrier metallayer 95.

By the process described above, obtained is a structure in which theinsulating film 92 corresponding to structure D in embodiment 2(A) isused as a gate insulating film.

In the process described above, it is possible to form an amorphousinsulating region in each of the entire upper region and the entirelower region of the insulating film 92, as shown in FIG. 11.

The TiO₂ crystal grain 93 may be a single crystal grain or an aggregateof a plurality of single crystal grains in which the same crystal faceorientations form an angle not larger than 10°, preferably not largerthan 5°. As described previously, where the angle formed by singlecrystal grains is not larger than 10°, the crystal grain interfaceenergy is small and, thus, the insulating properties are scarcelydeteriorated.

In this embodiment, the insulating film 92 is formed by oxidizing theTiN film 91. However, there are various modifications.

Titanium is used as a metal element forming the metal oxide contained inthe insulating film 92. In addition to Ti, it is also possible to useZr, Hf, Ta, Nb and Al.

Specifically, a TaN film is formed by a CVD method using a mixed gas ofTaCl₅/NH₃, a mixed gas of TaBr₅/NH₃ or a mixed gas of TaI₅/NH₃, followedby oxidizing the TaN film. As a result, formed are first insulatingregions 93 containing Ta₂O₅ crystal grains and a second insulatingregion 94 containing amorphous Ta₂O₅.

It is also possible to form a tantalum oxynitride film by a CVD methodusing a gas of [(CH₃)₂N]₅Ta, followed by substituting O for N byoxidizing the film.

Alternatively, a tantalum oxynitride film containing at least 1% of C isformed under the mixed gas noted above, or a Ta₂O₅ film containing atleast 1% of C is formed by using Ta(OC₂H₅), followed by oxidizing thesefilms with ozone to substitute O for C. By this method, formed is thefirst insulating regions 93 consisting of Ta₂O₅ crystal grains and thesecond insulating film 94 consisting of an amorphous Ta₂O₅. It should benoted that above described matters (containing at least 1% of C in thefilm, substituting O for N or C, oxidation using ozone,) are alsoavailable to other metals indicated above.

In the case of using niobium, a NbN film is formed by a CVD method usinga mixed gas of NbCl₅/NH₃, a mixed gas of NbBr₅/NH₃, or a mixed gas ofNbI₅/NH₃, followed by oxidizing the NbN film. As a result, formed arefirst insulating regions 93 containing Nb₂O₅ crystal grains and a secondinsulating region 94 containing amorphous Nb₂O₅.

In the case of using zirconium, a ZrN film is formed by a CVD methodusing a mixed gas of ZrCl₄/NH₃, a mixed gas of ZrBr₄/NH₃, a mixed gas ofZrI₄/NH₃, a mixed gas of Zr[N(C₂H₅)₂]₄/NH₃, or a mixed gas ofZr[N(CH₃)₂]₄/NH₃, followed by oxidizing the ZrN film. As a result,formed are first insulating regions 93 containing ZrO₂ crystal grainsand a second insulating region 94 containing amorphous ZrO₂.

Further, in the case of hafnium, a HfN film is formed by a CVD methodusing a mixed gas of HfCl₄/NH₃, a mixed gas of HfBr₄/NH₃, or a mixed gasof HfI₄/NH₃, followed by oxidizing the HfN film. As a result, formed arefirst insulating regions 93 containing HfO₂ crystal grains and a secondinsulating region 94 consisting of an amorphous HfO₂.

As described above, the first insulating regions 93 consisting ofcrystal grains of a metal oxide and the second insulating region 94consisting of an amorphous region of the metal oxide can be formedeasily by oxidizing a thin metal compound film containing a metalelement.

Incidentally, it is possible to apply the insulating film of embodiment2 to the processes shown in FIGS. 3A to 3F.

EMBODIMENT 3

Embodiment 3 of the present invention will now be described.

It is known to the art that, in performing a selective epitaxial growthof silicon, a silicon substrate fails to bear an ideal surface statebecause of the damage done by RIE, contamination with a gaseousimpurity, etc.

In forming a facet elevated source-drain structure, it was necessary touse a silicon oxide film for forming an insulating film on the side wallof the gate to bring about a facet in the step of epitaxial growth ofsilicon. Therefore, it was necessary to form a side wall by etching withRIE the silicon oxide film.

In embodiment 3, a side wall of the silicon oxide film can be formedwithout employing an RIE technology.

Embodiment 3(A)

Embodiment 3(A) will now be described with reference to the accompanyingdrawings.

In the first step, an element isolating region 101 consisting of anoxide film is formed within a silicon substrate 100 by using, forexample, an STI technology, as shown in FIG. 16A. The element isolatingregion 101 is formed as follows.

Specifically, a buffer oxide film (not shown) is formed as an etchingmask on the silicon substrate 100, followed by forming a silicon nitridefilm (not shown) on the buffer oxide film. Then, a pattern correspondingto an element region is formed by RIE using a resist pattern (not shown)as a mask. Further, that portion of the silicon substrate 100 whichcorresponds to the element isolating region 101 is etched using thepatterned silicon nitride film as a mask, followed by removing theresist.

In the next step, an insulating film such as a silicon oxide film isdeposited on the entire surface of the substrate 100 including theelement isolating region 101, followed by etching the insulating filmby, for example, a CMP (Chemical Mechanical Polish) to expose the uppersurface of the silicon nitride film acting as a stopper. Then, thesilicon nitride film and the buffer oxide film are removed to form anelement region and the element isolating region 101.

After formation of the element isolating region 101, a silicon nitridefilm 102 acting as a gate insulating film is formed by a CVD method onthe silicon substrate 100. It is desirable for the silicon nitride film102 to have a thickness not larger than 10 nm, particularly a thicknessof 3 to 6 nm. Used in this CVD step is, for example, a mixed gas ofNH₃/SiH₂Cl₂, a mixed gas of NH₃/SiCl₄, or a mixed gas of NH₃/Si₂Cl₆. Inthe case of using a mixed gas of NH₃/SiH₂Cl₂, a mixed gas of NH₃/SiCl₄ior a mixed gas of NH₃/Si₂Cl₆, the silicon nitride film 102 is formed at780° C., 700° C. or 450 to 700°C., respectively. In order to prevent anitride layer from being formed at the interface between the elementisolating region 101 and the silicon substrate 100, it is necessary toprevent ammonia from entering the interface between the elementisolating region 101 and the silicon substrate 100. Therefore, it isdesirable to form the silicon nitride film at a low temperature. Also,it is possible to form the silicon nitride film 100 on a native oxidefilm or a silicon oxide film formed by using chemicals as far as theunderlying layer has a thickness not larger than 3 nm.

In the next step, a polysilicon film or an amorphous silicon film 103doped with an N-type or P-type impurity such as phosphorus, arsenic orboron is formed in a thickness of 100 to 150 nm by a CVD method on thesilicon nitride film 102. Then, a silicon oxide film 104 is formed by aCVD method in a thickness of, for example, 50 nm on the polysilicon film103.

After formation of the silicon oxide film 104, a resist pattern, notshown, is formed by a lithography method on the silicon oxide film 104,followed by selectively removing by RIE the polysilicon film 103 and thesilicon oxide film 104 using the resist pattern as a mask. In this step,the silicon nitride film 102 is allowed to remain on the entire surfaceof the silicon substrate 100. As a result, formed is a gate structure ofa laminate structure consisting of the silicon nitride film 102, thepolysilicon film 103 and the silicon oxide film 104.

Then, an oxidizing treatment is applied to form a silicon oxide film(side wall) 105 selectively on the side surface of the polysilicon film103, as shown in FIG. 16B. In this step, a silicon oxide film is notformed on the silicon substrate 100 because the surface of the siliconsubstrate 100 is covered with the silicon nitride film 102.

After formation of the silicon oxide film 105, the silicon nitride film102 is removed by etching with a chemical solution such as a hotphosphoric acid, as shown in FIG. 16C. In this step, the temperature ofthe hot phosphoric acid should be controlled at room temperature to 180°C., preferably at about 160° C., in order to prevent the siliconsubstrate 100 and the element isolating region 101 from being etched. Bycontrolling the temperature of the hot phosphoric acid appropriately inremoving the silicon nitride film 102, it is possible to obtain at least10 of an etching selectivity ratio of the silicon nitride film 102 tothe silicon substrate 100 and to the silicon oxide film 104.

In the next step, a silicon or silicon-germanium film containing N- orP-type impurity in a concentration of 10¹⁹cm⁻³ or less is formed by aselective epitaxial growth to form an epitaxial silicon layer, followedby introducing an N- or P-type impurity by ion implantation into theepitaxial silicon layer in an average concentration of at least10¹⁹cm⁻³. It is possible to elevate the temperature to 900 to 1100° C.at a high temperature elevation rate of at least 150° C./sec and toapply a heat treatment for a period not longer than 60 seconds so as todope the impurity in the epitaxial layer. If the temperature for theheat treatment is lower than 900° C., the tail region of thedistribution of the ion-implanted impurity fails to be sharp, with theresult that it is difficult to maintain a concentration not lower than10¹⁹cm⁻³ to a depth of 50 nm and to control the depth of the pn junctionformed inside the silicon substrate 100 at 50 nm or less.

In this fashion, a silicon crystal is selectively grown by the selectiveepitaxial growth of silicon on only that region of the silicon substrate100 in which source-drain regions are to be formed so as to formelevated source-drain diffusion layers. The elevated source-draindiffusion layers are facet elevated source-drain diffusion layers 106 inwhich the height is gradually increased with increase in the distancefrom the lower end of the gate electrode. Then, the impurity containedin the facet elevated source-drain diffusion layers 106 is diffused by aheat treatment so as to form extension diffusion regions 107.

It should be noted that it is possible for a thin silicon oxide film tobe formed at the interface between the silicon nitride film 102 and thesilicon substrate 100 by the oxygen within the air atmosphere, by thetreatment with chemicals or by the heat treatment for forming thesilicon nitride film 102. To prevent the problem, it is desirable toremove the silicon nitride film 102 by a treatment with phosphoric acid,followed by removing the silicon oxide film by a treatment withhydrofluoric acid, in exposing the surface of the silicon substrate 100.It should be noted, however, that the silicon oxide film 105 and theelement isolating region 101 are also etched by the treatment withhydrofluoric acid. To prevent the problem, it is desirable to set thethickness of the silicon oxide film at 3 nm or less.

It should also be noted that a metal oxide film such as a titanium oxidefilm can be used in place of the silicon nitride film 102. Since thetitanium oxide film is insoluble in hydrofluoric acid and is soluble ina hot sulfuric acid, it is possible to obtain the effect similar to thatobtained in the case of using a silicon nitride film.

As described above, in embodiment 3(A), the insulating film such as asilicon nitride film formed on the substrate is removed by a treatmentwith phosphoric acid in place of an RIE treatment. Thus, it is possibleto form a structure in which the side wall of the gate is covered withthe silicon oxide film 105 without doing a damage to the siliconsubstrate surface on which the selective epitaxial growth is carriedout. Also, since phosphoric acid is used, the element isolating region101 is scarcely etched and, thus, the element isolating region is notretreated. It follows that the facet elevated source-drain diffusionlayer 106 can be formed easily even in the case where the side wall isformed of a silicon oxide film.

Embodiment 3(B)

In the MOSFET that is produced on a mass production basis, it isnecessary to lower the resistance of the gate electrode and thesource-drain diffusion layers, to increase the dielectric constant ofthe gate insulating film, and to form an N-type MOSFET and a P-typeMOSFET within the same wafer.

Embodiment 3(B) is directed to a MOSFET in which the gate is formed of ametal electrode, the gate insulating film is formed of a high dielectricconstant film, and a silicide film is formed on the source-draindiffusion layers.

In the first step, an element isolating region 111 consisting of anoxide film is formed within a silicon substrate 110 by using, forexample, an STI technology, as shown in FIG. 17A. Then, a siliconnitride film 112 having a thickness of 6 nm is formed on a siliconsubstrate 110 by a CVD method, as shown in FIG. 17A. Then, a polysiliconfilm 113 is formed in a thickness of 150 nm on the silicon nitride film112, followed by forming a silicon nitride film 114 in a thickness of 50nm on the polysilicon film 113. Since the polysilicon film 113constitutes a dummy gate that is to be removed later, the polysiliconfilm 113 need not be doped with an impurity.

In the next step, a resist pattern (not shown) is formed by alithography technology on the silicon nitride film 114, followed byetching the laminate structure consisting of the polysilicon film 113and the silicon nitride film 114 by an RIE technology using the resistpattern as a mask. In this step, the etching is controlled to permit thesilicon nitride film 112 to remain unremoved over the entire surface ofthe silicon substrate 110. As a result, formed is a gate structure of alaminate structure consisting of the silicon nitride film 112, thepolysilicon film 113 and the silicon nitride film 114.

In the next step, an oxidizing treatment is performed to form a siliconoxide film 115 selectively on the side surface of the polysilicon film113, as shown in FIG. 17B. In this step, a silicon oxide film is notformed on the surface of the silicon substrate 110 because the surfaceof the silicon substrate is covered with the silicon nitride film 112.

In the following manufacturing process, an N-type MOSFET and a P-typeMOSFET are formed separately. In FIGS. 17C to 17M, a region A denotes anN-type MOSFET and a region B denotes a P-type MOSFET.

As shown in FIG. 17C, a resist pattern 116 is formed selectively on theregion B by a lithography technology. Then, the silicon nitride film 112is removed by a wet etching with phosphoric acid using the resistpattern 116 as a mask so as to expose a surface 117 of the siliconsubstrate in region A. In this step, the silicon nitride film 114 isalso etched. However, the etching amount is negligible because thesilicon nitride film 112 is very thin.

In the next step, the resist 116 is removed by the etching with a mixedsolution consisting of sulfuric acid and hydrogen peroxide solution. Inthis step, a native oxide film (not shown) is formed on the surface 117of the silicon substrate in region A. However, the native oxide film isremoved by the hydrogen annealing at a high temperature that is carriedout in an apparatus for performing an epitaxial growth.

Then, silicon regions containing an N-type impurity such as phosphorusor arsenic are selectively formed on the silicon substrate surface 117in region A by a selective epitaxial growth, as shown in FIG. 17D. Sincethe silicon oxide film 115 is formed on the side surface of the gate,facet elevated source-drain diffusion layers 118 are formed by theepitaxial growth., The height of the facet elevated source-draindiffusion layer 118 is set not to be larger than the height of thepolysilicon film 113 forming the dummy gate. Then, the resist 116 isremoved.

In the next step, a thin silicon nitride film 119 having a thickness 3nm is formed on the entire surface, as shown in FIG. 17E.

Further, a resist pattern (not shown) is selectively formed in region Aby a lithography technology, as in the process shown in FIG. 17C. Then,the silicon nitride films 112 and 119 are removed by a wet etching withphosphoric acid using the resist pattern as a mask, with the result thata surface 120 of the silicon substrate is exposed in region B, as shownin FIG. 17F. In this step, the silicon nitride film 114 is also etched.However, since the silicon nitride film 112 is very thin, the etchingamount of the silicon nitride film 114 is negligibly small.

Further, the resist is removed with a mixed solution consisting ofsulfuric acid and hydrogen peroxide solution. In this step, a nativeoxide film (now shown) is formed on the surface 120 of the siliconsubstrate in region B. However, the native oxide film is removed by ahydrogen annealing at a high temperature that is carried out in anapparatus for performing an epitaxial growth. In this step, region A,which is covered with the silicon nitride film 119, is not affected atall.

In the next step, a P-type facet elevated source-drain diffusion layers121 are formed selectively on the surface 120 of the silicon substratein region B by a selective epitaxial growth of silicon containing aP-type impurity such as boron, as shown in FIG. 17G. In this step, aselective epitaxial growth does not take place in region A becauseregion A is covered with the silicon nitride film 119. The height of theP-type facet elevated source-drain diffusion layers 121 should not belarger than the height of the polysilicon film 113 constituting thedummy gate. Then, the silicon nitride film 119 is removed. In this step,the silicon nitride film 114 is also etched. However, the etching amountis negligibly small.

Then, a silicon nitride film 122 is formed by a CVD method in athickness of 40 nm on the entire surface, as shown in FIG. 17H, followedby applying a heat treatment so as to diffuse the impurities containedin the N-type facet source-drain diffusion layers 118 and the P-typefacet source-drain diffusion layers 121, thereby forming extensiondiffusion layers 123 on the silicon substrate 110. It is possible forthe N-type and P-type impurities to be different from each other in thediffusion rate, making it impossible to carry out the heat treatmentsimultaneously. In such a case, an N-type impurity alone having a lowdiffusion rate such as arsenic is diffused in the process shown in FIG.17E under a reasonably high temperature, followed by diffusing theP-type impurity having a high diffusion rate such as boron in theprocess shown in FIG. 17H.

After formation of the extension diffusion layers 123, a silicon oxidefilm 122 is etched back by a RIE technology, as shown in FIG. 17I. Bythis etching back, the upper surfaces of the facet elevated source-drainregions 118 and 121 are exposed to the outside. In this step, thesilicon oxide film 122 is left on the side wall of the gate and on theside wall of the facet elevated source-drain diffusion layers 118 and121.

In the next step, a metal film such as a titanium film or a cobalt filmis deposited on the entire surface, as shown in FIG. 17J, followed byapplying a salicide technology to permit a silicide layer 124 to beformed selectively on the upper surfaces of the facet elevatedsource-drain diffusion layers 118 and 121.

Further, an interlayer insulating film 125 consisting of an oxide filmis deposited by a CVD method on the entire surface, as shown in FIG.17K, followed by flattening the interlayer insulating film 125 by a CMPmethod so as to expose the surface of the silicon nitride film 114positioned on the dummy gate. It should be noted that the height of thefacet elevated source-drain diffusion layers 118 and 121 is not largerthan the height of the polysilicon film 113 constituting the dummy gate.As a result, the silicide film 124 formed on the facet elevatedsource-drain diffusion layers 118 and 121 is not exposed to the outside.

In the next step, the silicon nitride film 114 is selectively removed bya wet etching with phosphoric acid, with the interlayer insulating film125, as shown in FIG. 17L. Then, the polysilicon film 113 is selectivelyremoved by CDE or wet etching with the interlayer insulating film 125,the silicon oxide film 115 and the silicon nitride film 112. Further,the silicon nitride film 112 is selectively removed by etching withphosphoric acid, with the silicon nitride film 112 and the interlayerinsulating film 125. As a result, the dummy gate electrode is removed toform an opening for forming a gate electrode.

In the next step, a tantalum oxide film 126 as a high dielectricconstant film is formed in a thickness of 10 nm by a CVD method on theentire surface. The tantalum oxide film 126 thus formed acts as a gateinsulating film. Further, a titanium nitride film 127 is formed as abarrier film (reaction preventing film) in a thickness of 10 nm on thetantalum oxide film 126, as shown in FIG. 17M, followed by forming analuminum film 128 as a gate electrode on the titanium nitride film 127.As shown in the drawing, the gate electrode forming region is filledwith the aluminum film 128. Then, the aluminum film 128, the titaniumnitride film 127 and the tantalum oxide film 126 are flattened by a CMPtechnology so as to form a gate electrode.

In the embodiment described above, it is possible to apply a heattreatment at a high temperature in the step between the process offorming the silicon nitride film 112 shown in FIG. 17A and the processof removing the silicon nitride film 112 shown in FIG. 17L so as toconvert the lower portion of the silicon nitride film 112 into a siliconthermal nitride film. In this case, the silicon thermal nitride film isleft unremoved on the surface of the silicon substrate after removal ofthe silicon nitride film 112 in the process shown in FIG. 17L. It ispossible to use the silicon thermal nitride film or a silicon thermaloxynitride film resulting from oxidation of the silicon thermal nitridefilm as the gate insulating film. It is also possible to use a laminatestructure consisting of the silicon thermal nitride film or siliconthermal oxynitride film and a high dielectric constant film formed onthe nitride film or the oxynitride film as the gate insulating film.

It is also possible to use a metal oxide film such as a titanium oxidefilm in place of the silicon nitride film 112. Since the titanium oxidefilm is insoluble in hydrofluoric acid and soluble in a hot sulfuricacid, the titanium oxide film produces an effect similar to thatproduced by the silicon nitride film.

As described above, the silicon nitride film 112 is formed on thesilicon substrate in embodiment 3(B). Each of these silicon nitride filmand silicon oxide film can be selectively removed by a wet etching.Since the silicon nitride film 112 can be removed by a wet etching, thesurface 120 of the silicon substrate 110 can be exposed to the outsidewithout doing damage to the silicon substrate surface 120. It should benoted that the silicon oxide film is not removed in the step of removingthe silicon nitride film by a wet etching with phosphoric acid. Also, inthe step of removing a part of the silicon oxide film by a wet etching,the silicon nitride film can be used as a barrier film of the siliconoxide film.

Incidentally, the gate insulating film described previously inconjunction with embodiment 1 and 2 can be used in embodiment 3.

EMBODIMENT 4

Embodiment 4 of the present invention will now be described.

It has been clarified that, in forming the elevated source-draindiffusion layers by the epitaxial growth after formation of theextension diffusion layers, it is difficult to make the N-type diffusionlayer and the P-type diffusion layer equal to each other in thicknessbecause of the difference in the impurity contained in the N-typediffusion layer and the P-type diffusion layer. In embodiment 4, theextension diffusion layers are formed after formation of the elevatedsource-drain diffusion layers by the epitaxial growth.

Embodiment 4(A)

In the first step, an element isolating region (not shown) is formed byan STI technology within a silicon substrate 200, as shown in FIG. 18A.Then, the impurity concentration in a channel portion of the transistoris controlled, as desired, by injecting an impurity into a region inwhich a transistor is to be formed.

In the next step, a buffer oxide film (not shown) is formed on thesilicon substrate 200, followed by forming a polysilicon film 201 on thebuffer oxide film. It is possible to form an amorphous silicon film inplace of the polysilicon film 201. Then, a silicon nitride film 202 isformed on the polysilicon film 201, followed by forming a resist pattern(not shown) on the silicon nitride film 202. Further, an anisotropicetching is applied with the resist pattern used as a mask so as toselectively remove the silicon nitride film 202 and the polysilicon film201 and, thus, to form a dummy gate. Then, the resist is removed.

In the next step, the dummy gate is oxidized as desired, followed byforming a silicon nitride film in a thickness of 10 nm on the entiresurface. Then, the silicon nitride film is anisotropically etched toform a side wall 203 consisting of a very thin silicon nitride film onthe side surface of the dummy gate, as shown in FIG. 18B.

After formation of the very thin silicon nitride side wall 203, thesurface of the silicon substrate 200 is washed with a dilutehydrofluoric acid and by a hot hydrogen treatment at, for example, 900°C. for 5 minutes, followed by forming an epitaxial silicon layer 204having a thickness of 30 nm by a selective epitaxial growth of silicon,as shown in FIG. 18C. In this step, the upper surface of the dummy gateis covered with the silicon nitride film 202 and, thus, an epitaxialgrowth of silicon does not take place on the dummy gate. Also, since theside surface of the dummy gate is covered with the silicon nitride film203, a facet is not generated in the epitaxial silicon layer.

In the next step, impurity ions are implanted to form extensiondiffusion layers 205, as shown in FIG. 18D. Since presence of theepitaxial silicon layer 204 provides an allowance in the depth directionin performing the ion implantation, the extension diffusion layers 205can be formed by the ordinary ion implantation technology. For example,an N-type diffusion layer can be formed under an accelerating energy of20 keV and at a dose of 1×10¹⁵cm⁻² using arsenic as an impurity. Theannealing for activating the extension diffusion layer 205 can beperformed at, for example, 800° C. for 10 seconds. Phosphorus can alsobe used as an impurity in place of arsenic. For forming a P-typediffusion layer, used is boron or boron fluoride (BF₂). Since thesilicon nitride side wall 203 is formed thin, the extension diffusionlayer 205 can be formed to reach sufficiently the edge of the dummygate.

Then, a silicon oxide film is formed as required as an etching stopper,followed by forming a silicon nitride film 50 nm thick on the siliconoxide film.

In the next step, the silicon oxide film is anisotropically etched toform a silicon oxide side wall 206 and a silicon nitride side wall 207,as shown in FIG. 18E. Further, source-drain diffusion layers 208 areformed by ion implantation using the silicon nitride side wall 207 as amask, as shown in FIG. 18F. The annealing for activating thesource-drain diffusion layers 208 is performed at 1,000° C. for 10seconds.

Further, an interlayer insulating film 209 is formed on the entiresurface, followed by flattening the interlayer insulating film 209 by aCMP to expose the upper surface of the silicon nitride film 202positioned on the dummy gate, as shown in FIG. 18G. It is possible toemploy an etching back method in place of the CMP.

In the next step, the silicon nitride films 202, 203 and 207 are removedby the treatment with a hot phosphoric acid until the upper surface ofthe polysilicon film 201 is exposed to the outside, as shown in FIG.18H. Further, the polysilicon film 201 is removed by a CDE method toform a trench 210, as shown in FIG. 18I, followed by removing thesilicon oxide film (not shown) formed as a buffer layer by the treatmentwith a dilute hydrofluoric acid so as to expose the surface of thesilicon substrate 200. After removal of the dummy gate, the localthreshold voltage can be controlled by means of ion implantation throughthe buffer oxide film.

In the next step, a gate insulating film 211 is formed by oxidizing thesurface of the exposed silicon substrate 200 or by depositing aninsulating film, e.g., tantalum oxide. A metal oxide other than tantalumoxide can also be used for forming the gate insulating film 211 as faras the metal oxide has a high dielectric constant.

Then, a titanium nitride film 212 is formed as a barrier film (reactionpreventing film), followed by forming a tungsten film 213 as a metalfilm on the titanium nitride film 212 such that the trench 210 is filledwith the tungsten film 213. It is also possible to use aluminum, copper,etc. for forming the metal film. Further, it is possible to use tungstennitride or tantalum nitride for forming the reaction preventing film.Incidentally, in the case of using a P-containing polysilicon forforming the electrode, the reaction preventing film need not be formed.

Then, flattening is performed by a CMP method to form a gate electrode214 within the trench 210. It is also possible to employ a patterningand an etching for forming the gate electrode in place of the flatteningtreatment by a CMP method. The ordinary process for forming a transistorcan be employed in the subsequent steps. However, a transistor of a highperformance can be formed by adding the step of removing the side wallas described in the following.

Specifically, the silicon-nitride side walls 203 and 207 are removed asshown in FIG. 18K, followed by forming an interlayer insulating film 218consisting of, for example, TEOS on the entire surface. Where, forexample, the height of the gate electrode 214 is 30 nm and the thicknessof the silicon nitride side wall 203 is 20 nm (condition 1), the trench217 is filled substantially completely with the interlayer insulatingfilm 218, as shown in FIG. 18L. On the other hand, where, for example,the height of the gate electrode 214 is 100 nm, and the thickness of thesilicon nitride side wall 203 is 10 nm (condition 2), the trench 217 isnot filled completely with the interlayer insulating film 218 becausethe aspect ratio of the height of the gate electrode 214 to thethickness of the side wall 20 is high, as shown FIG. 18M. As result,cavities 219 are formed. Presence of the cavity 219 is effective fordecreasing the dielectric constant.

Where a silicon oxide side wall 207 a is formed on a silicon nitrideside wall 206 a as shown in FIG. 19A, the silicon nitride side walls 203and 206 a are removed to form a trench 217 a as shown in FIG. 19B. Undercondition 1 given above, the trench 217 a is filled with the interlayerinsulating film 218, as shown in FIG. 19C. Under condition 2 givenabove, however, a cavity 219 is formed as shown in FIG. 19D.

It is possible to form an epitaxial silicon layer 215 or 216 by aselective epitaxial growth as shown in FIG. 20A or FIG. 21A after theprocess shown in FIG. 18E and before the ion implantation. Then,source-drain diffusion layers 208 are formed by ion implantation asshown in FIG. 20B or FIG. 21B.

Silicon is consumed in the silicidation reaction. Therefore, formationof the epitaxial silicon layer 215 imparts an allowance in terms of thedepth of the source-drain regions, making it possible to carry out theion implantation in a high concentration, which is effective fordecreasing the contact resistance.

As described above, an epitaxial silicon layer is formed beforeformation of an extension diffusion layer in this embodiment. Therefore,where N-type and P-type transistors are formed within the samesubstrate, the epitaxial layers can be controlled easily at the samethickness. It is also possible to prevent the extension diffusion layerfrom being expanded by the heat treatment in the step of the epitaxialgrowth.

Embodiment 4(B)

This embodiment is directed to a transistor using an ordinarypolysilicon gate electrode that does not require a damascene gateprocess.

In the first step, an element region and an element isolating region(not shown) are formed within a silicon substrate 220 as in embodiment4(A), followed by controlling the threshold value of the transistor byimplanting impurity ions, as required. Then, the surface of the siliconsubstrate 220 is oxidized to form a gate oxide film 221 on the elementregion, followed by forming a polysilicon film 221 on the gate oxidefilm 221, as shown in FIG. 22A. The polysilicon film 222 thus formed isselectively removed by an anisotropic etching using a resist pattern(not shown) as a mask to form a gate electrode. The gate electrode maybe formed of amorphous silicon in place of polysilicon. It is alsopossible to use polysilicon doped in advance with an impurity such asphosphorus. Further, a laminate structure consisting of a polysiliconfilm and a tungsten film deposited on the polysilicon film can also beused as a gate electrode.

In the next step, the etching damage is removed by oxidizing the gateelectrode in a thickness of about 5 nm, followed by forming a siliconnitride film in a thickness of 10 nm.

The silicon nitride film thus formed is anisotropically etched to leavea silicon nitride side wall 223 unremoved on the side surface of thepolysilicon film 222, as shown in FIG. 22B. Then, a treatment with adilute hydrofluoric acid and a hot hydrogen treatment are carried out toexpose and cleanse those portions of a surface of the silicon substrate200 which correspond to the source-drain regions.

In the next step, an epitaxial silicon layer 224 is formed in athickness of 30 nm on the substrate 200 by a selective epitaxial growth,as shown in FIG. 22C. It is possible for a silicon layer to grow on theupper surface of the polysilicon film 222. However, the transistorcharacteristics are not affected by the silicon layer thus grown. Itshould also be noted that, since the silicon nitride film 223 is formedon the side wall of the polysilicon film 222, a facet is not generatedin the epitaxial silicon layer 224.

In the next step, imipurity ions are implanted into the epitaxialsilicon layer 224 to form an extension diffusion layer 225, as shown inFIG. 22D. In the case of forming an N-type diffusion layer, arsenic ionsare implanted as an impurity under an accelerating energy of 20 keV andat a dose of 1×10¹⁵cm⁻². The annealing for activating the extensiondiffusion layer 225 is performed at, for example, 800° C. for 10seconds. Then, a silicon oxide film is formed as desired as an etchingstopper, followed by forming a silicon nitride film in a thickness of 50nm on the silicon oxide film.

In the next step, a silicon oxide side wall 226 and a silicon nitrideside wall 227 are formed on the side surfaces of the polysilicon film222 by an anisotropic etching, as shown in FIG. 22E, followed by formingsource-drain diffusion layers 228 by means of ion implantation using thesilicon nitride side wall 227 as a mask, as shown in FIG. 22F. Theannealing for activating the source-drain diffusion layers 228 and thegate electrode is performed at, for example, 1,000° C. for 10 seconds.

It is possible to form an epitaxial silicon layer by a selectiveepitaxial growth after the process shown in FIG. 22E and before the ionimplantation. It should be noted that silicon is consumed by thesilicidation reaction. Therefore, the epitaxial silicon layer formed inadvance serves to replenish silicon during the silicidation reaction. Itshould also be noted that it is possible to inject an impurity into thegate electrode consisting of polysilicon so as to use theimpurity-containing polysilicon layer as a gate wiring.

As described above, an epitaxial silicon layer is formed beforeformation of the extension diffusion layer in embodiment 4(B) as inembodiment 4(A). As a result, an effect similar to that produced inembodiment 4(A) can also be produced in embodiment 4(B).

Incidentally, the insulating film described previously in conjunctionwith embodiment 1 and 2 can also be; used in embodiment 4.

EMBODIMENT 5

Embodiment 5 of the present invention will now be described.

It is known to the art that, in forming a gate insulating film afterformation of a silicide film, the metal in the silicide film is migratedinto the gate insulating film so as to deteriorate the reliability ofthe gate insulating film.

In this embodiment, a gate insulating film is formed first, followed byforming a silicide film. In other words, the gate insulating film isformed in this embodiment before formation of a silicide film on thesource-drain diffusion layers. Also, in this embodiment, a gatestructure of a metal single layer is formed by a damascene gate process.

In the first step, an element isolating region 301 is formed within asemiconductor substrate 300, as shown in FIG. 23A, followed by forming agate oxide film 302 as a dummy gate in a thickness of 6 nm on thesemiconductor substrate 300. Then, a polysilicon film 303 in a thicknessof 250 nm is formed on the gate oxide film 302, followed by forming asilicon nitride film 304 in a thickness of 50 nm on the polysilicon film303. Further, the polysilicon film 303 and the silicon nitride film 304are selectively removed by using a resist pattern (not shown) as a maskso as to form a dummy gate of a laminate structure.

After formation of the dummy gate, extension diffusion regions 305 areformed within the semiconductor substrate by ion implantation of animpurity. Then, a silicon nitride film is formed on the entire surface,followed by anisotropically etching the silicon nitride film to form asilicon nitride side wall 306 having a width of 40 nm on the sidesurface of the dummy gate.

In the next step, the gate oxide film on the substrate is removed by thetreatment with hydrofluoric acid so as to expose those portions of thesurface of the semiconductor substrate 300 which are positionedcorresponding to the source-drain regions, as shown in FIG. 23B. Then,epitaxial silicon layers are selectively grown on the exposed surfacesof the semiconductor substrate 300 to form elevated source-draindiffusion layers 307 having a height of 70 nm from the surface of thesemiconductor substrate 300. In this step, a facet is not formed in theelevated source-drain diffusion layer 307 because the silicon nitridefilm 306 is formed on the side surface of the dummy gate.

Then, source-drain diffusion regions (not shown) are formed by an ionimplantation technology. Incidentally, it is possible to form theextension diffusion regions 305 by solid phase diffusion of an impurityin the step of forming the source-drain diffusion layers in place offorming the extension diffusion regions 305 in the process shown in FIG.23A.

In the next step, an interlayer insulating film 308 is formed on theentire surface, as shown in FIG. 23C. Then, the interlayer insulatingfilm 308 is flattened by a CMP method so as to expose the upper surfacesof the silicon nitride films 304 and 306 to the outside. It should benoted that the upper surfaces of the elevated source-drain diffusionlayers 307 are positioned lower than the upper surface of the dummy gateand, thus, the upper surfaces of the source-drain diffusion layers 307are not exposed to the outside.

Then, the silicon nitride film 304 is removed by the treatment withphosphoric acid, followed by removing the polysilicon film 303 by a CDEmethod or a wet etching. Further, the dummy gate oxide film 302 isremoved by the treatment with hydrofluoric acid so as to form an openingin the gate-forming portion.

In the next step, a gate insulating film 309 is formed by an oxidizingtreatment, a CVD method or deposition of a material having a highdielectric constant using a CVD method, as shown in FIG. 23D. In thisstage, it is possible to form a gate insulating film into which a metalis not migrated because a silicide film is not formed on thesource-drain regions. Also, even if an ion implantation treatment and anactivating treatment are performed after formation of the gate-formingportion, a metal does not migrate into the gate insulating film so as toprevent the reliability of the gate insulating film from being lowered.It follows that it is possible to apply an ion implantation into thechannel region after formation of the gate-forming portion. Since a hightemperature step such as a step of forming the source-drain diffusionlayers is not included in the subsequent process, it is possible to forma channel structure having a very sharp impurity depth profile.

In the next step, a titanium nitride film 310 is formed as a barrierfilm (reaction preventing film) on the entire surface, followed byforming an aluminum layer 311 providing a metal gate electrode materialby a CVD method on the titanium nitride film 310, as shown FIG. 23E.

Then, a flattening treatment is applied by a CMP method to the aluminumlayer 311, the titanium nitride film 310, the gate insulating film 309and the silicon nitride side wall 306 so as to expose the upper surfaceof the elevated source-drain diffusion layers 307 to the outside and toform a gate electrode 312, as shown in FIG. 23F.

In the next step, an oxidizing treatment is applied to form an aluminumoxide film 313 and a titanium oxide film 314 on the surface of the gateelectrode 312. Also formed is a silicon oxide film 315 on the elevatedsource-drain diffusion layer 307.

In the next step, the silicon oxide film 315 on the elevatedsource-drain diffusion layer 307 is removed by the treatment withhydrofluoric acid, as shown in FIG. 23H. In this step, the aluminumoxide film 313 and the titanium oxide film 314, which are insoluble inhydrofluoric acid, are not removed.

Then, a metal film 316 is formed on the entire surface, as shown in FIG.23I. The metal film 316 is formed of a noble metal forming a silicide ata temperature lower than the melting point of aluminum. To be morespecific, the metal film 316 is formed of, for example, palladium,nickel, platinum or cobalt. It is also possible to use an alloycontaining at least one of these noble metals.

Then, a silicide film 317 is selectively formed by a heat treatment, asshown in FIG. 23J. In this step, a silicidation reaction does not takeplace on the surface of the gate electrode 312 because the aluminumoxide film 313 and the titanium oxide film 314 are formed on the surfaceof the gate electrode 312. As a result, the silicidation reaction takesplace selectively on the surface of the elevated source-drain diffusionlayer 307.

In order to prevent the leakage current, the silicide film 317 is formedin a height of at least 60 nm from the bottom of the extension diffusionregion 305. Also, the depth of the extension diffusion region 305 fromthe surface of the silicon substrate 300 is set at 50 nm to 60 nm.

In the next step, the metal film 316 that is not subjected to asilicidation reaction is removed, as shown in FIG. 23J. The metal film316 can be removed by a wet etching. Alternatively, the unreacted metalfilm 316 can also be removed by a flattening process such as a CMPprocess because the unreacted metal film 316 is formed on a flatsurface.

As described above, the unreacted metal film in the salicide process canbe removed by a flattening process such as a CMP process. Therefore, itis possible to eliminate the problem inherent in the wet etching such asthe metal residue, the disappearance of the gate electrode or thedissolution of the silicide, making it possible to remove easily variousunreacted metals. It follows that it is possible to use metals such aspalladium, though such metals were not used in the past in thesemiconductor device because it is difficult to achieve a selectiveetching in the wet etching process.

Palladium silicide (Pd₂Si) is advantageous in some respects overtitanium silicide or cobalt silicide used nowadays. It should be notedthat a ratio of D_(silicon), which represents the thickness of thesilicon film consumed in forming palladium silicide, to D_(silicide),which represents the thickness of the formed silicide film, i.e.,D_(silicon)/D_(silicide), is about 0.5, whereas, the corresponding ratiois about 1 in each of a titanium silicide film and a cobalt silicidefilm. What should be noted is that the amount of silicon consumed whennoble metals such as palladium form a silicide is smaller than thatconsumed when titanium or cobalt forms a silicide. With increase in theamount of silicon consumed in forming a silicide, the morphology at theinterface between silicon and silicide is deteriorated, as shown in FIG.24, leading to an increased leakage current through the diffusion layer.Therefore, the increase in the leakage current can be prevented by usingpalladium silicide.

Incidentally, the silicon consumption in forming a silicide can besuppressed in the case of using platinum in addition to palladium. TheD_(silicon)/D_(silicide) ratio for platinum is about 0.7.

Embodiment 5 is advantageous in the step of forming a contact hole afterthe step shown in FIG. 23J. Specifically, since the structure shown inFIG. 23J has a flat upper surface, the interlayer insulating film can beformed easily. Also, the interlayer insulating film can be formed thin.As a result, it is possible to diminish the aspect ratio of the contacthole, making it possible to fill easily the contact hole. Also, it ispossible to omit the flattening process of the interlayer insulatingfilm using CMP and the re-flow process of the interlayer insulatingfilm.

FIG. 25 is a graph showing by Weibull plot the reliability of a gateinsulating film measured by TDDB (Time Dependent Dielectric Breakdown).In the graph of FIG. 25, the amount of charge injected into the gateinsulating film is plotted on the abscissa, with the cumulative failurebeing plotted on the ordinate. The data of the prior art and the data ofthis embodiment are shown in the graph of FIG. 25.

FIG. 25 shows that, in the conventional Weibull plot, the total chargeamount at which the failure takes place is nonuniform among the chips inthe same wafer. This indicates that chips in which the failure of thegate tends to take place are present in the same wafer, leading to a lowreliability of the product. The failure of the gate is caused by a metalmigrating into the gate oxide film or into the interface with the oxidefilm.

On the other hand, in the Weibull plot for this embodiment of thepresent invention, the total charge amount at which the failure of thegate takes place is substantially uniform in any chip within the samewafer. In other words, this embodiment of the present invention makes itpossible to prevent a metal from migrating into the gate oxide film orinto the interface with the oxide film so as to improve the reliabilityof the product.

In embodiment 5, aluminum is used as an electrode material of the metalgate. Alternatively, it is also possible to use other metals such astitanium, zirconium, hafnium, tantalum, niobium, and vanadium as well asnitrides of these metals. In this case, formed by oxidation are titaniumoxide, zirconium oxide, hafnium oxide, tantalum oxide, niobium oxide andvanadium oxide.

Embodiment 5 is applied to a MOSFET of a damascene structure. Inaddition, embodiment 5 can be applied to an ordinary MOSFET.

As described above, a silicide film is formed, in embodiment 5 by adamascene gate process, after formation of a gate insulating film,making it possible to prevent the metal contained in the silicide filmfrom migrating into the gate insulating film.

Incidentally, the insulating film described previously in conjunctionwith embodiment 1 and 2 can also be used in embodiment 5.

Additional advantages and modifications will readily occur to thoseskilled in the art. Therefore, the invention in its broader aspects isnot limited to the specific details and representative embodiments shownand described herein. Accordingly, various modifications may be madewithout departing from the spirit or scope of the general inventiveconcept as defined by the appended claims and their equivalents.

1. A method of manufacturing a semiconductor device, comprising: forminga first insulating film, selected from a silicon oxide film, a siliconnitride film, and a silicon oxynitride film, on a semiconductorsubstrate; forming a metal compound film on the first insulating film;forming a second insulating film comprising a metal oxide film or ametal silicate film by oxidizing said metal compound film; and formingan electrode on said second insulating film, wherein said metal compoundfilm does not contain tungsten.
 2. The method of manufacturing asemiconductor device according to claim 1, wherein said metal compoundfilm has a thickness not larger than 5 nm.
 3. The method ofmanufacturing a semiconductor device according to claim 1, whereinformation of said metal compound film and formation of said secondinsulating film by oxidation of the metal compound film are repeated aplurality of times.
 4. The method of manufacturing a semiconductordevice according to claim 1, wherein said metal compound film isselected from a metal nitride film, an oxygen-containing metal nitridefilm, a silicon-containing metal nitride film, a metal nitride filmcontaining both oxygen and silicon, a metal carbide film, anoxygen-containing metal carbide film, a silicon-containing metal carbidefilm, a metal carbide film containing both oxygen and silicon, a metalcarbonitride film, an oxygen-containing metal carbonitride film, asilicon-containing metal carbonitride film, and a metal carbonitridefilm containing both oxygen and silicon.
 5. The method of manufacturinga semiconductor device according to claim 1, wherein said metal compoundfilm contains at least one metal selected from titanium, zirconium,hafnium, tantalum, niobium, aluminum, yttrium and cerium.
 6. A method ofmanufacturing a semiconductor device comprising: forming a metalcompound film directly or indirectly on a semiconductor substrate;forming a metal-containing insulating film comprising a metal oxide filmor a metal silicate film by oxidizing said metal compound film; andforming an electrode on said metal-containing insulating film, whereinsaid metal-containing insulating film comprises a plurality of firstinsulating regions formed of grains containing a metal oxide of a metalelement contained in said metal compound film and a second insulatingregion formed of an amorphous insulating material, and each of saidfirst insulating regions is formed in said second insulating region, andwherein said metal compound film does not contain tungsten.
 7. Themethod of manufacturing a semiconductor device according to claim 6,wherein said metal compound film contains a metal element forming saidmetal oxide and silicon, said first insulating region contains a crystalof said metal oxide, and said second insulating region contains silicon,oxygen and a metal element forming said metal oxide.
 8. The method ofmanufacturing a semiconductor device according to claim 6, wherein saidmetal compound film contains a first metal element forming said metaloxide and a second metal element differing from said first metalelement, said first insulating region contains a crystal of said metaloxide, and said second insulating region contains oxygen and said secondmetal element.
 9. The method of manufacturing a semiconductor deviceaccording to claim 6, wherein said metal compound film contains a metalelement forming said metal oxide, said first insulating region is formedof crystal grains of said metal oxide, and said second insulating regionis formed of an amorphous region of said metal oxide.
 10. The method ofmanufacturing a semiconductor device according to claim 6, wherein saidmetal compound film has a thickness not larger than 5 nm.
 11. The methodof manufacturing a semiconductor device according to claim 6, whereinsaid metal compound film is selected from a metal nitride film, anoxygen-containing metal nitride film, a silicon-containing metal nitridefilm, a metal nitride film containing both oxygen and silicon, a metalcarbide film, an oxygen-containing metal carbide film, asilicon-containing metal carbide film, a metal carbide film containingboth oxygen and silicon, a metal carbonitride film, an oxygen-containingmetal carbonitride film, a silicon-containing metal carbonitride film,and a metal carbonitride film containing both oxygen and silicon. 12.The method of manufacturing a semiconductor device according to claim 6,wherein said metal compound film contains at least one metal selectedfrom titanium, zirconium, hafnium, tantalum, niobium, aluminum, yttrium,and cerium.